Salicylic acid derivatives of the formula I,

The present invention relates to salicylic acid derivatives of the formula I
where the index and the substituents are as follows:
X is halogen, NO2, cyano, C1-C4-alkyl or C1-C4-alkoxy;
m is 0, 1, 2 or 3, it being possible for the substituents X to differ from each other if n is greater than 1;
A is OH, C1-C4-alkoxy, NH2, NHCH3 or N(CH3)2;
R1 is phenyl, naphthyl, C3-C10-cycloalkyl, 5-membered or 6-membered hetaryl or 5-membered or 6-membered heterocyclyl containing one to three N atoms and/or one O or S atom or one or two O and/or S atoms, the ring systems being unsubstituted or substituted by one to three radicals Ra:
Ra is cyano, nitro, amino, aminocarbonyl, aminothiocarbonyl, halogen, hydroxyl, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkyloxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, phenyl, phenoxy, benzyl, benzyloxy, 5- or 6-membered heterocyclyl, 5- or 6-membered hetaryl, 5- or 6-membered hetaryloxy, C(xe2x95x90NORxcex1)xe2x80x94ORxcex2 or OC(Rxcex1)2xe2x80x94C(Rxcex2)xe2x95x90NORxcex2,
xe2x80x83the cyclic radicals, in turn, being unsubstituted or substituted by one to three radicals Rb:
Rb is cyano, nitro, halogen, hydroxyl, amino, aminocarbonyl, aminothiocarbonyl, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, phenyl, phenoxy, phenylthio, benzyl, benzyloxy, 5- or 6-membered heterocyclyl, 5- or 6-membered hetaryl, 5- or 6-membered hetaryloxy or C(xe2x95x90NORxcex1)xe2x80x94ORxcex2;
xe2x80x83Rxcex1, Rxcex2 is hydrogen or C1-C6-alkyl;
R2 is hydrogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-alkylthio,
xe2x80x83the hydrocarbon radicals being unsubstituted or partially or fully halogenated or it being possible for them to have attached to them one to three groups Rc:
Rc is halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylcarbonyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino,
xe2x80x83di-C1-C6-alkylamino, C2-C6-alkenyl, C3-C6-alkenyloxy, C3-C6-alkynyloxy or C1-C4-alkylenedioxy which can be halogenated.
Furthermore, the invention relates to processes for the preparation of these compounds, to compositions comprising them, and to their use for controlling harmful fungi.
WO-A 97/08135, DE-A 197 10 609 and WO-A 99/27783 disclose acylaminosalicylamides for controlling harmful fungi.
However, their action is unsatisfactory in many cases.
It is an object of the invention to provide compounds with an improved action.
We have found that this object is achieved by the compounds defined at the outset. Moreover, there have been found processes for their preparation, compositions comprising them and methods of controlling phytopathogenic harmful fungi using the compounds I.
The compounds of the formula I differ from those of the prior art by the hydrazide group.
The compounds of the formula I show an increased efficacy against harmful fungi compared with the known compounds.
Compounds of the formula I can be prepared for example starting from alkyl salicylates of the formula II where A is C1-C4-alkoxy and Z is a protecting group which can be eliminated under acidic conditions, such as, for example, an acetyl group.
Compounds of the formula II can be obtained by free-radical halogenation under generally customary conditions, especially advantageously by bromination with N-bromosuccinimide (NBS) using azobisisobutyronitrile (AIBN) as free-radical initiator with exposure to light [cf. J. Amer. Chem. Soc., Vol. 71 (1949), p. 2137 et seq; ibid., Vol. 90 (1968), p. 1797 et seq]. Compounds of the formula II where A is methoxy, Z is acetyl and Hal is bromine are preferred.
This reaction is usually carried out at temperatures of from 20xc2x0 C. to 150xc2x0 C., preferably from 50xc2x0 C. to 100xc2x0 C., in an inert organic solvent [cf. Can. J. Chem., Vol. 33 (1955), p. 1819; J. Org. Chem., Vol. 49 (1984), p. 2158].
Suitable solvents are halogenated hydrocarbons such as carbon tetrachloride, chloroform and chlorobenzene. Mixtures of the solvents mentioned may also be used.
In general, the starting materials are reacted with each other in equimolar amounts. It may be advantageous for the yield to employ NBS in an excess based on II.
The starting materials II required for the preparation of the compounds I are commercially available, known from the literature [Bull. Soc. Chim. Fr., Vol. 9 (1966), p. 2821; Biotechnol. Lett., Vol. 15 (1993), p. 469; J. Fluorine Chem., Vol. 74 (1995), p. 69] or can be prepared in accordance with the literature cited.
The dihalo compounds of the formula III are oxidized with elimination of the protecting group Z under acidic conditions to give the keto compounds IV.
This reaction is usually carried out at temperatures of from 20xc2x0 C. to 150xc2x0 C., preferably from 20xc2x0 C. to 100xc2x0 C., in an inert organic solvent in the presence of an acid (cf. Org. Synth., Vol. 20 (1940), p. 92].
Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide, N,N-dimethylformamide and N,N-dimethylacetamide, especially preferably methanol, ethanol and n-propanol. Mixtures of the solvents mentioned may also be used.
Acids and acidic catalysts which are used are inorganic acids such as hydrofluoric acid, aqueous hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, iron(III) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(II) chloride, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
In general, the acids are employed in catalytic amounts, but they may also be used in equimolar amounts, in an excess or, if appropriate, as solvents.
To prepare compounds I where A is NH2, NHCH3 or N(CH3)2, salicylic esters IV are reacted with ammonia or methylamine to give salicylamides of the formula IV.1 where R3 is hydrogen or methyl; the reaction with dimethylamine gives compounds of the formula IV.3:
This reaction is usually carried out at temperatures of from 20xc2x0 C. to 150xc2x0 C., preferably from 20xc2x0 C. to 100xc2x0 C., in an inert organic solvent [cf. Arch. Pharm. (1982), p. 941].
Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile, alcohols, and dimethyl sulfoxide, N,N-dimethylformamide and N,N-dimethylacetamide, especially preferably N,N-dimethylformamide and N,N-dimethylacetamide. Mixtures of the solvents mentioned may also be used.
In general, the starting materials are reacted with each other in equimolar amounts. It may be advantageous for the yield to employ the amine in an excess based on IV.
The imino group is usually eliminated from IV.1 at temperatures of from 20xc2x0 C. to 150xc2x0 C., preferably from 20xc2x0 C. to 100xc2x0 C., in an inert organic solvent in the presence of an acid [cf. J. Chem. Soc. (1957), p. 3807; J. Org. Chem., Vol. 6 (1941), p. 489].
Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethyl sulfoxide, N,N-dimethylformamide and N,N-dimethylacetamide, especially preferably methanol, ethanol and n-propanol. Mixtures of the solvents mentioned may also be used.
Acids and acidic catalysts which are used are inorganic acids such as hydrofluoric acid, aqueous hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, iron(III) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(II) chloride, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
To prepare compounds of the formula I where A is hydroxyl, the alkyl esters of the formula IV are hydrolyzed by customary methods to give the salicylic acids of the formula IV.4 [cf. Organikum [Organic chemistry], 16th Ed., pp. 415 and 622, VEB Deutscher Verlag der Wissenschaften, Berlin 1985]. This reaction is usually carried out at temperatures of from 10xc2x0 C. to 80xc2x0 C., preferably 20xc2x0 C. to 60xc2x0 C., in an inert organic solvent in the presence of a base, such as alkali metal hydroxides or alkaline earth metal hydroxides, in particular sodium hydroxide or potassium hydroxide.
Depending on the form which radical A in formula I takes, compounds of the formulae IV, IV.2, IV.3 or IV.4 are reacted with hydrazides of the formula V to give compounds of the formula I.
This reaction is usually carried out at temperatures of from 20xc2x0 C. to 150xc2x0 C., preferably from 20xc2x0 C. to 80xc2x0 C., in an inert organic solvent in the presence of an acid [cf. Org. Prep. Proced. Int., Vol. 30 (1998), p. 177; CH-A 661 276].
Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, nitrites, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethyl sulfoxide, N,N-dimethylformamide and N,N-dimethylacetamide, especially preferably methanol, ethanol, n-propanol, isopropanol or N,N-dimethylformamide. Mixtures of the solvents mentioned may also be used.
Acids and acidic catalysts which are used are inorganic acids such as hydrofluoric acid, aqueous hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, iron(III) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(II) chloride, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
In general, the acids are employed in catalytic amounts, but they may also be used in equimolar amounts, in an excess or, if appropriate, as solvents.
In general, the starting materials are reacted with each other in equimolar amounts. It may be advantageous for the yield to employ V in an excess based on IV.
The reaction mixtures are worked up in the customary manner, for example by mixing with water, phase separation and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colorless or pale brown, viscous oils which are purified or freed from volatile components under reduced pressure and at a moderately elevated temperature. If the intermediates and end products are obtained as solids, they may also be purified by recrystallization or digestion.
If individual compounds I cannot be obtained by the above-described routes, they can be prepared by derivatizing the compounds I.
Upon their preparation, the compounds I may be obtained, owing to their Cxe2x95x90C and Cxe2x95x90N double bonds, as E/Z isomer mixtures which can be separated in the customary manner, for example by crystallization or chromatography, to give the individual compounds.
If, upon synthesis, isomer mixtures are obtained, separation is, however, not absolutely necessary since some of the individual isomers may be converted into each other during preparation for use, or upon use (for example with exposure to light, acids or bases). Similar conversions may also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus to be controlled.
In the definitions of the symbols in the above formulae, collective terms were used which generally represent the following substituents:
halogen: fluorine, chlorine, bromine and iodine;
alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4 or 6 carbon atoms, for example C1-C6-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;
haloalkyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above), it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, for example C1-C2-haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
alkoxy: straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above) which are bonded to the skeleton via an oxygen atom (xe2x80x94Oxe2x80x94);
alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4 or 6 carbon atoms and one double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
alkynyl: straight-chain or branched hydrocarbon groups having 2 to 4 or 6 carbon atoms and one triple bond in any position, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;
cycloalkyl: monocyclic, saturated hydrocarbon groups having 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
5- or 6-membered heterocyclyl contains, in addition to carbon ring members, one to three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, e.g. 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl;
5-membered heteroaryl contains one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-membered heteroaryl ring groups which may contain, in addition to carbon atoms, one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, e.g. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl and 1,3,4-triazol-2-yl;
6-membered heteroaryl contains one to three, or one to four, nitrogen atoms: 6-membered heteroaryl ring groups which, in addition to carbon atoms, may contain one to three, or one to four, nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl;
alkylene: divalent unbranched chains of 1 to 4 CH2 groups, e.g. CH2, CH2CH2, CH2CH2CH2 and CH2CH2CH2CH2;
alkylenedioxy: divalent unbranched chains of 1 to 3 CH2 groups, both valences being bonded to the skeleton by an oxygen atom, e.g. OCH2O, OCH2CH2O and OCH2CH2CH2O.
Especially preferred with regard to the intended use of the salicylic acid derivatives of the formula I are the following meanings of the substituents, in each case alone or in combination:
Especially preferred are compounds of the formula I where A is methyl, methoxy, hydroxyl, amino and methylamino.
Particularly preferred are compounds IA:
In addition, especially preferred compounds I are those where the index m is zero; these compounds are described by the formula IB:
Especially preferred compounds I are furthermore those where R2 is methyl.
Moreover, especially preferred compounds I are those where (X)m is in the para position relative to the phenol OH group and is halogen, NO2, CN and C1-C4-alkoxy, in particular 4-chloro, 4-bromo and 4-NO2.
Particularly preferred compounds I are also those where R1 is cyclohexyl and phenyl which is unsubstituted or substituted by one to three radicals Ra, particularly phenyl. In the case of compounds where R1 is cyclohexyl, the substituent Ra may be in the E- or Z-position relative to the Cxe2x80x94R1 bond.
Especially preferred compounds I are those where R1 is pyrazole, pyrimidine, pyridine, pyrazine and thiophene, each of which is unsubstituted or substituted by one to three radicals Ra.
Also preferred are compounds I where Ra is chlorine, bromine, nitro, cyano, methyl, ethyl, n- and iso-propyl, n- and sec- and tert-butyl and phenyl, the aromatic ring being unsubstituted or substituted by one or two radicals from the group consisting of chlorine, bromine, nitro, cyano and methyl.
Equally especially preferred are compounds I where R2 is hydrogen, methyl, methoxy and cyano, in particular hydrogen and methyl.
The especially preferred embodiments of the intermediates with regard to the variables correspond to those of radicals A, (X)m, R1 and R2 of the formula I.
Particularly preferred with regard to their use are the compounds I which are compiled in the tables which follow. In addition, the groups mentioned in the tables for a substituent constitute an especially preferred embodiment of the substituent in question, independently of the combination in which they are mentioned.
Table 1
Compounds of the formula I where m is zero, A is methoxy and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 2
Compounds of the formula I where m is zero, A is methoxy and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 3
Compounds of the formula I where m is zero, A is methoxy and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 4
Compounds of the formula I where m is zero, A is methoxy and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 5
Compounds of the formula I where (X)m is 3-chloro, A is methoxy and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 6
Compounds of the formula I where (X)m is 3-chloro, A is methoxy and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 7
Compounds of the formula I where (X)m is 3-chloro, A is methoxy and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 8
Compounds of the formula I where (X)m is 3-chloro, A is methoxy and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 9
Compounds of the formula I where (X)m is 4-chloro, A is methoxy and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 10
Compounds of the formula I where (X)m is 4-chloro, A is methoxy and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 11
Compounds of the formula I where (X)m is 4-chloro, A is methoxy and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 12
Compounds of the formula I where (X)m is 4-chloro, A is methoxy and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 13
Compounds of the formula I where (X)m is 5-chloro, A is methoxy and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 14
Compounds of the formula I where (X)m is 5-chloro, A is methoxy and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 15
Compounds of the formula I where (X)m is 5-chloro, A is methoxy and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 16
Compounds of the formula I where (X)m is 5-chloro, A is methoxy and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 17
Compounds of the formula I where (X)m is 3-bromo, A is methoxy and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 18
Compounds of the formula I where (X)m is 3-bromo, A is methoxy and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 19
Compounds of the formula I where (X)m is 3-bromo, A is methoxy and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 20
Compounds of the formula I where (X)m is 3-bromo, A is methoxy and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 21
Compounds of the formula I where (X)m is 4-bromo, A is methoxy and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 22
Compounds of the formula I where (X)m is 4-bromo, A is methoxy and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 23
Compounds of the formula I where (X)m is 4-bromo, A is methoxy and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 24
Compounds of the formula I where (X)m is 4-bromo, A is methoxy and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 25
Compounds of the formula I where (X)m is 5-bromo, A is methoxy and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 26
Compounds of the formula I where (X)m is 5-bromo, A is methoxy and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 27
Compounds of the formula I where (X)m is 5-bromo, A is methoxy and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 28
Compounds of the formula I where (X)m is 5-bromo, A is methoxy and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 29
Compounds of the formula I where (X)m is 3-nitro, A is methoxy and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 30
Compounds of the formula I where (X)m is 3-nitro, A is methoxy and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 31
Compounds of the formula I where (X)m is 3-nitro, A is methoxy and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 32
Compounds of the formula I where (X)m is 3-nitro, A is methoxy and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 33
Compounds of the formula I where (X)m is 4-nitro, A is methoxy and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 34
Compounds of the formula I where (X)m is 4-nitro, A is methoxy and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 35
Compounds of the formula I where (X)m is 4-nitro, A is methoxy and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 36
Compounds of the formula I where (X)m is 4-nitro, A is methoxy and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 37
Compounds of the formula I where (X)m is 5-nitro, A is methoxy and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 38
Compounds of the formula I where (X)m is 5-nitro, A is methoxy and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 39
Compounds of the formula I where (X)m is 5-nitro, A is methoxy and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 40
Compounds of the formula I where (X)m is 5-nitro, A is methoxy and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 41
Compounds of the formula I where m is zero, A is amino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 42
Compounds of the formula I where m is zero, A is amino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 43
Compounds of the formula I where m is zero, A is amino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 44
Compounds of the formula I where m is zero, A is amino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 45
Compounds of the formula I where (X)m is 3-chloro, A is amino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 46
Compounds of the formula I where (X)m is 3-chloro, A is amino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 47
Compounds of the formula I where (X)m is 3-chloro, A is amino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 48
Compounds of the formula I where (X)m is 3-chloro, A is amino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 49
Compounds of the formula I where (X)m is 4-chloro, A is amino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 50
Compounds of the formula I where (X)m is 4-chloro, A is amino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 51
Compounds of the formula I where (X)m is 4-chloro, A is amino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 52
Compounds of the formula I where (X)m is 4-chloro, A is amino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 53
Compounds of the formula I where (X)m is 5-chloro, A is amino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 54
Compounds of the formula I where (X)m is 5-chloro, A is amino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 55
Compounds of the formula I where (X)m is 5-chloro, A is amino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 56
Compounds of the formula I where (X)m is 5-chloro, A is amino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 57
Compounds of the formula I where (X)m is 3-bromo, A is amino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 58
Compounds of the formula I where (X)m is 3-bromo, A is amino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 59
Compounds of the formula I where (X)m is 3-bromo, A is amino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 60
Compounds of the formula I where (X)m is 3-bromo, A is amino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 61
Compounds of the formula I where (X)m is 4-bromo, A is amino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 62
Compounds of the formula I where (X)m is 4-bromo, A is amino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 63
Compounds of the formula I where (X)m is 4-bromo, A is amino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 64
Compounds of the formula I where (X)m is 4-bromo, A is amino and R2 is isopropyl, and the radical R1 for each compound corresponds to one line of Table A
Table 65
Compounds of the formula I where (X)m is 5-bromo, A is amino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 66
Compounds of the formula I where (X)m is 5-bromo, A is amino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 67
Compounds of the formula I where (X)m is 5-bromo, A is amino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 68
Compounds of the formula I where (X)m is 5-bromo, A is amino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 69
Compounds of the formula I where (X)m is 3-nitro, A is amino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 70
Compounds of the formula I where (X)m is 3-nitro, A is amino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 71
Compounds of the formula I where (X)m is 3-nitro, A is amino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 72
Compounds of the formula I where (X)m is 3-nitro, A is amino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 73
Compounds of the formula I where (X)m is 4-nitro, A is amino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 74
Compounds of the formula I where (X)m is 4-nitro, A is amino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 75
Compounds of the formula I where (X)m is 4-nitro, A is amino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 76
Compounds of the formula I where (X)m is 4-nitro, A is amino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 77
Compounds of the formula I where (X)m is 5-nitro, A is amino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 78
Compounds of the formula I where (X)m is 5-nitro, A is amino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 79
Compounds of the formula I where (X)m is 5-nitro, A is amino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 80
Compounds of the formula I where (X)m is 5-nitro, A is amino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 81
Compounds of the formula I where m is zero, A is methylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 82
Compounds of the formula I where m is zero, A is methylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 83
Compounds of the formula I where m is zero, A is methylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 84
Compounds of the formula I where m is zero, A is methylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 85
Compounds of the formula I where (X)m is 3-chloro, A is methylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 86
Compounds of the formula I where (X)m is 3-chloro, A is methylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 87
Compounds of the formula I where (X)m is 3-chloro, A is methylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 88
Compounds of the formula I where (X)m is 3-chloro, A is methylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 89
Compounds of the formula I where (X)m is 4-chloro, A is methylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 90
Compounds of the formula I where (X)m is 4-chloro, A is methylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 91
Compounds of the formula I where (X)m is 4-chloro, A is methylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 92
Compounds of the formula I where (X)m is 4-chloro, A is methylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 93
Compounds of the formula I where (X)m is 5-chloro, A is methylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 94
Compounds of the formula I where (X)m is 5-chloro, A is methylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 95
Compounds of the formula I where (X)m is 5-chloro, A is methylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 96
Compounds of the formula I where (X)m is 5-chloro, A is methylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 97
Compounds of the formula I where (X)m is 3-bromo, A is methylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 98
Compounds of the formula I where (X)m is 3-bromo, A is methylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 99
Compounds of the formula I where (X)m is 3-bromo, A is methylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 100
Compounds of the formula I where (X)m is 3-bromo, A is methylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 101
Compounds of the formula I where (X)m is 4-bromo, A is methylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 102
Compounds of the formula I where (X)m is 4-bromo, A is methylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 103
Compounds of the formula I where (X)m is 4-bromo, A is methylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 104
Compounds of the formula I where (X)m is 4-bromo, A is methylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 105
Compounds of the formula I where (X)m is 5-bromo, A is methylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 106
Compounds of the formula I where (X)m is 5-bromo, A is methylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 107
Compounds of the formula I where (X)m is 5-bromo, A is methylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 108
Compounds of the formula I where (X)m is 5-bromo, A is methylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 109
Compounds of the formula I where (X)m is 3-nitro, A is methylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 110
Compounds of the formula I where (X)m is 3-nitro, A is methylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 111
Compounds of the formula I where (X)m is 3-nitro, A is methylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 112
Compounds of the formula I where (X)m is 3-nitro, A is methylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 113
Compounds of the formula I where (X)m is 4-nitro, A is methylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 114
Compounds of the formula I where (X)m is 4-nitro, A is methylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 115
Compounds of the formula I where (X)m is 4-nitro, A is methylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 116
Compounds of the formula I where (X)m is 4-nitro, A is methylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 117
Compounds of the formula I where (X)m is 5-nitro, A is methylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 118
Compounds of the formula I where (X)m is 5-nitro, A is methylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 119
Compounds of the formula I where (X)m is 5-nitro, A is methylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 120
Compounds of the formula I where (X)m is 5-nitro, A is methylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 121
Compounds of the formula I where m is zero, A is dimethylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 122
Compounds of the formula I where m is zero, A is dimethylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 123
Compounds of the formula I where m is zero, A is dimethylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 124
Compounds of the formula I where m is zero, A is dimethylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 125
Compounds of the formula I where (X)m is 3-chloro, A is dimethylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 126
Compounds of the formula I where (X)m is 3-chloro, A is dimethylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 127
Compounds of the formula I where (X)m is 3-chloro, A is dimethylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 128
Compounds of the formula I where (X)m is 3-chloro, A is dimethylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 129
Compounds of the formula I where (X)m is 4-chloro, A is dimethylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 130
Compounds of the formula I where (X)m is 4-chloro, A is dimethylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 131
Compounds of the formula I where (X)m is 4-chloro, A is dimethylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 132
Compounds of the formula I where (X)m is 4-chloro, A is dimethylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 133
Compounds of the formula I where (X)m is 5-chloro, A is dimethylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 134
Compounds of the formula I where (X)m is 5-chloro, A is dimethylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 135
Compounds of the formula I where (X)m is 5-chloro, A is dimethylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 136
Compounds of the formula I where (X)m is 5-chloro, A is dimethylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 137
Compounds of the formula I where (X)m is 3-bromo, A is dimethylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 138
Compounds of the formula I where (X)m is 3-bromo, A is dimethylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 139
Compounds of the formula I where (X)m is 3-bromo, A is dimethylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 140
Compounds of the formula I where (X)m is 3-bromo, A is dimethylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 141
Compounds of the formula I where (X)m is 4-bromo, A is dimethylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 142
Compounds of the formula I where (X)m is 4-bromo, A is dimethylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 143
Compounds of the formula I where (X)m is 4-bromo, A is dimethylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 144
Compounds of the formula I where (X)m is 4-bromo, A is dimethylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 145
Compounds of the formula I where (X)m is 5-bromo, A is dimethylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 146
Compounds of the formula I where (X)m is 5-bromo, A is dimethylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 147
Compounds of the formula I where (X)m is 5-bromo, A is dimethylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 148
Compounds of the formula I where (X)m is 5-bromo, A is dimethylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 149
Compounds of the formula I where (X)m is 3-nitro, A is dimethylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 150
Compounds of the formula I where (X)m is 3-nitro, A is dimethylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 151
Compounds of the formula I where (X)m is 3-nitro, A is dimethylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 152
Compounds of the formula I where (X)m is 3-nitro, A is dimethylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 153
Compounds of the formula I where (X)m is 4-nitro, A and R2 are hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 154
Compounds of the formula I where (X)m is 4-nitro, A is dimethylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 155
Compounds of the formula I where (X)m is 4-nitro, A is dimethylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 156
Compounds of the formula I where (X)m is 4-nitro, A is dimethylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 157
Compounds of the formula I where (X)m is 5-nitro, A is dimethylamino and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 158
Compounds of the formula I where (X)m is 5-nitro, A is dimethylamino and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 159
Compounds of the formula I where (X)m is 5-nitro, A is dimethylamino and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 160
Compounds of the formula I where (X)m is 5-nitro, A is dimethylamino and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 161
Compounds of the formula I where m is zero, A is hydroxyl and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 162
Compounds of the formula I where m is zero, A is hydroxyl and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 163
Compounds of the formula I where m is zero, A is hydroxyl and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 164
Compounds of the formula I where m is zero, A is hydroxyl and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 165
Compounds of the formula I where (X)m is 3-chloro, A is hydroxyl and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 166
Compounds of the formula I where (X)m is 3-chloro, A is hydroxyl and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 167
Compounds of the formula I where (X)m is 3-chloro, A is hydroxyl and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 168
Compounds of the formula I where (X)m is 3-chloro, A is hydroxyl and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 169
Compounds of the formula I where (X)m is 4-chloro, A is hydroxyl and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 170
Compounds of the formula I where (X)m is 4-chloro, A is hydroxyl and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 171
Compounds of the formula I where (X)m is 4-chloro, A is hydroxyl and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 172
Compounds of the formula I where (X)m is 4-chloro, A is hydroxyl and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 173
Compounds of the formula I where (X)m is 5-chloro, A is hydroxyl and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 174
Compounds of the formula I where (X)m is 5-chloro, A is hydroxyl and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 175
Compounds of the formula I where (X)m is 5-chloro, A is hydroxyl and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 176
Compounds of the formula I where (X)m is 5-chloro, A is hydroxyl and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 177
Compounds of the formula I where (X)m is 3-bromo, A is hydroxyl and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 178
Compounds of the formula I where (X)m is 3-bromo, A is hydroxyl and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 179
Compounds of the formula I where (X)m is 3-bromo, A is hydroxyl and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 180
Compounds of the formula I where (X)m is 3-bromo, A is hydroxyl and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 181
Compounds of the formula I where (X)m is 4-bromo, A is hydroxyl and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 182
Compounds of the formula I where (X)m is 4-bromo, A is hydroxyl and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 183
Compounds of the formula I where (X)m is 4-bromo, A is hydroxyl and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 184
Compounds of the formula I where (X)m is 4-bromo, A is hydroxyl and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 185
Compounds of the formula I where (X)m is 5-bromo, A is hydroxyl and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 186
Compounds of the formula I where (X)m is 5-bromo, A is hydroxyl and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 187
Compounds of the formula I where (X)m is 5-bromo, A is hydroxyl and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 188
Compounds of the formula I where (X)m is 5-bromo, A is hydroxyl and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 189
Compounds of the formula I where (X)m is 3-nitro, A is hydroxyl and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 190
Compounds of the formula I where (X)m is 3-nitro, A is hydroxyl and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 191
Compounds of the formula I where (X)m is 3-nitro, A is hydroxyl and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 192
Compounds of the formula I where (X)m is 3-nitro, A is hydroxyl and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 193
Compounds of the formula I where (X)m is 4-nitro, A and R2 are hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 194
Compounds of the formula I where (X)m is 4-nitro, A is hydroxyl and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 195
Compounds of the formula I where (X)m is 4-nitro, A is hydroxyl and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 196
Compounds of the formula I where (X)m is 4-nitro, A is hydroxyl and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
Table 197
Compounds of the formula I where (X)m is 5-nitro, A is hydroxyl and R2 is hydrogen, and the radical R1 for each compound corresponds to one line of Table A
Table 198
Compounds of the formula I where (X)m is 5-nitro, A is hydroxyl and R2 is methyl, and the radical R1 for each compound corresponds to one line of Table A
Table 199
Compounds of the formula I where (X)m is 5-nitro, A is hydroxyl and R2 is methoxy, and the radical R1 for each compound corresponds to one line of Table A
Table 200
Compounds of the formula I where (X)m is 5-nitro, A is hydroxyl and R2 is cyano, and the radical R1 for each compound corresponds to one line of Table A
The compounds I are suitable as fungicides. They are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them act systemically, and they can be employed in crop protection as foliar- and soil-acting fungicides.
They are especially important for controlling a large number of fungi on a variety of crop plants such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soybean, coffee, sugar cane, grapevine, fruit species, ornamentals and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants.
Specifically, they are suitable for controlling the following plant diseases:
Alternaria species on vegetables and fruit,
Botrytis cinerea (gray mold) on strawberries, vegetables, ornamentals and grapevines,
Cercospora arachidicola on peanuts,
Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
Erysiphe graminis (powdery mildew) on cereals,
Fusarium- and Verticillium species on a variety of plants,
Helminthosporium species on cereals,
Mycosphaerella species on bananas and peanuts,
Phytophthora infestans on potatoes and tomatoes,
Plasmopara viticola on grapevines,
Podosphaera leucotricha on apples,
Pseudocercosporella herpotrichoides on wheat and barley,
Pseudoperonospora species on hops and cucumbers,
Puccinia species on cereals,
Pyricularia oryzae on rice,
Rhizoctonia species on cotton, rice and turf,
Septoria nodorum on wheat,
Uncinula necator on grapevines,
Ustilago species on cereals and sugar cane, and
Venturia species (scab) on apples and pears.
Moreover, the compounds I are suitable for controlling harmful fungi such as Paecilomyces variotii in the protection of materials (e.g. wood, paper, paint dispersions, fibers and fabrics) and in the protection of stored products.
The compounds I are applied by treating the fungi, or the plants, seed, materials or the soil to be protected against fungal infection, with a fungicidally active amount of the active ingredients. Application can be effected both before and after infection of the materials, plants or seeds by the fungi.
In general, the fungicidal compositions comprise from 0.1 to 95, preferably 0.5 to 90, % by weight of active ingredient.
When used in crop protection, the application rates are from 0.01 to 2.0 kg of active ingredient per ha, depending on the nature of the desired effect.
In the treatment of seeds, amounts of active ingredient of from 0.001 to 0.1 g, preferably 0.01 to 0.05 g, are generally required per kilogram of seed.
When used in the protection of materials or stored products, the application rate of active ingredient depends on the nature of the field of application and on the desired effect. Application rates conventionally used in the protection of materials are, for example, from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active ingredient per cubic meter of material treated.
The compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular purpose; it is intended to ensure in each case a fine and uniform distribution of the compound according to the invention.
The formulations are prepared in a known manner, e.g. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as cosolvents if water is used as the diluent. Auxiliaries which are suitable are essentially: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanones), amines (e.g. ethanolamine, N,N-dimethylformamide) and water; carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali metal and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ether, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol or formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, e.g. coated granules, impregnated granules, homogeneous granules, can be prepared by binding the active ingredients on solid carriers. Examples of solid carriers are mineral earths such as silicas, silica gels, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
The following are examples of formulations:
I. 5 parts by weight of a compound according to the invention are mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dust which comprises 5% by weight of the active ingredient.
II. 30 parts by weight of a compound according to the invention are mixed intimately with a mixture of 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel. This gives a formulation of active ingredient with good adhesion properties (active ingredient content 23% by weight).
III. 10 parts by weight of a compound according to the invention are dissolved in a mixture composed of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide, 2 parts by weight of calcium dodecylbenzenesulfonate and 2 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (active ingredient compound 9% by weight).
IV. 20 parts by weight of a compound according to the invention are dissolved in a mixture composed of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (active ingredient content 16% by weight).
V. 80 parts by weight of a compound according to the invention are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill (active ingredient content 80% by weight).
VI. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-xcex1-pyrrolidone, which gives a solution which is suitable for use in the form of microdrops (active ingredient content 90% by weight).
VII. 20 parts by weight of a compound according to the invention are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion comprising 0.02% by weight of the active ingredient.
VIII. 20 parts by weight of a compound according to the invention are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-xcex1-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture comprising 0.1% by weight of the active ingredient.
The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active ingredients according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
The active ingredients may also be used successfully in the ultra-low-volume method (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives.
Various types of oils, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate immediately prior to use (tank mix). These agents can be admixed with the agents according to the invention in a weight ratio of 1:10 to 10:1.
In the use form as fungicides, the compositions according to the invention can also be present together with other active ingredients, e.g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides frequently results in a broader fungicidal spectrum of action.
The following list of fungicides together with which the compounds according to the invention can be used is intended to illustrate the possible combinations, but not to impose any limitation:
sulfur, dithiocarbamates and their derivatives, such as iron(III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfide, ammonia complex of zinc (N,N-ethylenebisdithiocarbamate), ammonia complex of zinc (N,Nxe2x80x2-propylenebisdithiocarbamate), zinc (N,Nxe2x80x2-propylenebisdithiocarbamate), N,Nxe2x80x2-polypropylenebis(thiocarbamoyl) disulfide;
nitro derivatives, such as dinitro(1-methylheptyl)phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl 5-nitro-isophthalate;
heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethyl phthalimidophosphonothioate, 5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo[4,5-b]-quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole, 2-(4-thiazolyl)benzimidazole, N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide;
N-dichlorofluoromethylthio-Nxe2x80x2,Nxe2x80x2-dimethyl-N-phenylsulfodiamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine-2-thiol 1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 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, N-cyclohexyl-2,5-dimethylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine-2,2,2-trichloroethyl acetal, piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide, 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane;
amines such as 2,6-dimethyl-N-tridecylmorpholine or its salts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine, N-[3-(p-tert-butylphenyl)-2-methylpropyl]piperidine;
azoles such as 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-Nxe2x80x2-imidazolylurea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol, (2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole, xcex1-(2-chlorophenyl)-xcex1-(4-chlorophenyl)-5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene, 1,2-bis(3-methoxycarbonyl-2-thioureido)benzene;
strobilurins such as methyl E-methoxyimino-[xcex1-(o-tolyloxy)-o-tolyl]acetate, methyl E-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, N-methyl-E-methoxy imino-[xcex1-(2-phenoxyphenyl)]acetamide, N-methyl E-methoxyimino-[xcex1-(2,5-dimethylphenoxy)-o-tolyl]acetamide; methyl E-2-{2-[2-trifluoromethylpyridyl-6-]oxymethyl]phenyl}-3-methoxyacrylate, methyl (E,E)-methoximino-{2-[1-(3-trifluoromethylphenyl)ethylideneaminooxymethyl]phenyl}acetate, methyl N-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]-oxymethyl}phenyl)N-methoxycarbamate,
anilinopyrimidines such as N-(4,6-dimethylpyrimidin-2-yl)aniline, N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline, N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline;
phenylpyrroles such as 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile;
cinnamamides such as 3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloylmorpholine;
and a variety of fungicides such as dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide, hexachlorobenzene, methyl N-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate, DL-N-(2,6-dimethylphenyl)-N-(2xe2x80x2-methoxyacetyl)alanine methyl ester, N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-amino-butyrolactone, DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester, 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-isopropylcarbamoylhydantoin, N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide, 1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole, 2,4-difluoro-xcex1-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol, N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, 1-((bis(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole.

Salicylic acid derivatives, processes for their preparation, compositions comprising them, and their use

Abstract: where the index and the substituents have the following meanings:

Abstract: X is halogen, NO2, cyano, alkyl or alkoxy;

Abstract: m is 0, 1, 2 or 3, it being possible for the substituents X to be different from each other if n is greater than 1;

Abstract: A is OH, alkoxy, NH2, NHCH3 or N(CH3)2;

Abstract: R1 is phenyl, naphthyl, cycloalkyl, 5-membered or 6-membered hetaryl or 5-membered or 6-membered heterocyclyl, comprising one to three N atoms and/or one O or S atom or one or two O and/or S atoms, the ring systems being unsubstituted or substituted;

Abstract: R2 is hydrogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy or alkylthio,

Abstract: processes for the preparation of these compounds, compositions comprising them, and their use for controlling harmful fungi.


A pipe coupling wherein an elastic sleeve receives the end portions of two pipes and has a partition which extends between the end portions of the pipes. The sleeve is surrounded by a split ring in the form of a band whose end portions are spot welded to strip-shaped female components of a device for tightening the band around the sleeve. The median sections of the female components define with the band two aligned passages for the shank of a bolt whose head can be rotated to move it nearer to a nut which meshes with the shank and extends into a centrally located corrugation of the band. The head and nut flank the median sections of the two female components of the tightening device. Each end section of each of the two female components is welded to the adjacent portions of the band at two or more locations which are disposed at different distances from the gap between the two components.

The present invention relates to flexible pipe couplings in general, and more particularly to improvements in flexible pipe couplings of the type wherein an elastic sleeve which can consist of rubber or an equivalent material surrounds the end portions of the pipes which are to be coupled to each other and is surrounded by a clamp serving to bias the internal surface of the sleeve against the external surfaces of the end portions of the pipes.
The aforementioned commonly owned copending patent application Ser. No. 664,346 discloses a flexible pipe couling wherein the sleeve has a ring-shaped partition which extends from its internal surface and between the end faces of the two pipes and the clamp includes a band in the form of a split ring with L-shaped projections at its ends. The first leg of each projection is bonded to the external surface of the respective end of the split ring, and the second leg of each projection extends radially outwardly from the split ring and has a hole for the shank of a bolt which mates with a nut and is used to move the second legs of the two projections nearer to each other in order to tighten the split ring around the elastic sleeve. The marginal portions of the split ring slope toward the external surfaces of the respective pipes and overlie the respective open ends of the sleeve, and the central portion of the split ring is formed with a corrugation which extends into a groove in the external surface of the sleeve.
The flexible pipe coupling which is disclosed in the copending patent application Ser. No. 664,346 can be used with advantage to establish a fluidtight connection between drain pipes which consist of cast iron. The L-shaped projections of its clamp consist of sheet metal and are welded to the split ring. The clamp is intended to tighten the sleeve around the end portions of the pipe with a force which suffices to ensure that the sleeve can withstand substantial stresses tending to move the two pipes substantially axially and away from each other, i.e., to extract the end portions of the pipes from the sleeve. It has been found that the ability of a pipe coupling with L-shaped projections at the ends of the split ring to resist extraction of the end portions of the pipes from the sleeve is rather limited, primarily because the second legs of the L-shaped projections tend to bend in response to rotation of the nut and shank relative to each other in order to reduce the distance between the second legs and such bending takes place before the split ring can clamp the sleeve with a force which is required to ensure that the sleeve is held in requisite frictional engagement with the external surfaces of the pipes. The thickness and strength of the L-shaped projections cannot be increased at will, not only because this would contribute to the bulk, weight and cost of the clamp but also because the first legs of relatively thick projections cannot be readily spot welded to the respective ends of the split ring. Spot welding is the currently preferred mode of bonding the projections to the split ring. Still further, relatively thick, heavy, stiff and bulky projections would adversely influence the ability of the split ring to ensure the establishment of a reliable seal between the two pipes during bending of the sleeve, i.e., on movement of one of the pipes to a position in which its axis is inclined with reference to the axis of the other pipe. More specifically, relatively heavy and thick projections would prevent the aforementioned corrugation of the split ring from compensating for eventual tolerances in the outer diameters of the pipes, and such heavy and thick projections would further prevent adequate flexing of the sleeve under the above outlined circumstances, i.e., when the axis of one of the pipes which are coupled to each other is inclined with reference to the axis of the other pipe.
The tightening or clamping force which is furnished by the bolt and nut and is applied to the central portions of the second legs is transmitted primarily or to a larger extent to the marginal portions of the split ring diametrically opposite the two projections. The marginal portions are bent inwardly toward the external surfaces of the respective pipes and they apply to the sleeve radial forces which are greater in the region diametrically opposite the projections than at the end portions of the split ring. Such non-uniform distribution of radial forces, as considered in the circumferential direction of the marginal portions of the split ring, reduces the reliability of the clamp as concerns its ability to resist axial stresses, i.e., a movement of the end portions of the pipes away from each other. Premature bending of the second legs relative to the first legs of the projections in response to tightening of the clamp around the sleeve is undesirable because the second legs are likely to come into actual abutment with each other, and to thus prevent further tightening of the clamp around the sleeve, before the sleeve undergoes a deformation which suffices to prevent leakage of the conveyed fluid and/or ready extraction of the end portions of the pipes from the sleeve. Non-uniform distribution of radial forces, as considered in the circumferential direction of the marginal portions of the split ring, is undesirable on the ground that this reduces the likelihood of the establishment of a predictable and reliable seal between the internal surface of the sleeve and the external surfaces of the pipes, on the ground that it prevents the sleeve from furnishing an adequate sealing action when one of the pipes is moved to a position in which its axis is inclined relative to the axis of the other pipe, and on the ground that the pipes can be readily moved axially and away from each other, e.g., in response to increasing pressure of the confined fluid medium. The likelihood of unsatisfactory sealing action and/or insufficient resistance of the sleeve to axial movements of the pipes away from each other is especially pronounced when the clamp employs a single bolt and nut and when the width of the band-shaped split ring is relatively small, e.g., in the range of between 35 and 50 mm.


The subject mater herein relates to data processing and, more particularly, to encryption acceleration. Various embodiments herein provide devices and systems including a standardized encryption application programming interface embedded in firmware to perform encryption services. Some such embodiments move encryption operations away from operating system processes into firmware. As a result, encryption operations are generally accelerated.

As data security becomes more an more important to individuals and enterprises, encryption of data, both stored and transient data, has become prevalent. However, software operations to encrypt and decrypt data are extremely resource intensive. This commonly slows performance of devices performing the encryption operations. Slowed performance is especially visible in instances where data stored on hard disks is encrypted, such as in encrypted volumes. In such instances, as operating systems are loaded, it is not uncommon for at least some portions of operating system instructions to be decrypted prior to execution. However, the operating system needs to be decrypted in the pre-boot environment which is very resource-poor. As a result, the decryption of the operating system extends boot time considerably. With Logical-Block-Addressing ("LBA") based encryption utilized in full-volume encryption, coupled with ever-larger disks, such as two terabyte disks today and ten terabyte disks expected by 2010, LBA based encryption and other encryption technologies create usability concerns from long install operations, long machine reboots, and the like.
Further, as network bandwidth availability increases, more and more data in larger and larger files is being sent over networks. At the same time, encryption of data transmitted over networks is often necessary. As a result, data transmission latency is increasing due to software encryption and decryption operations performed on the data.


The present invention provides a card connector that can be loaded on a double-sided printed circuit board and allows intergration of components using common components. A first and a second housing 1, 2 have a pair of cranked hook-shaped projections 17. A first and a second covering plate 5, 6 have a cranked hook-shaped opening 57. The first covering plate 5 can be joined to the second housing 2 by reversing in a left-right direction the first covering plate 5. The second covering plate 6 can be joined to the first housing 1 by reversing in a left-right direction the second covering plate 6. The first and the second housings 1, 2, and the first and the second covering plates 5, 6 can be used as common parts, respectively.

1. Field of the Invention
The present invention relates to a card connector. Particularly, the present invention relates to a structure of a card connector that can be mounted on both surfaces of a printed circuit board.
2. Related Art
In recent years, a memory card driving device having a two-tier driving device, to which memory cards can be loaded above and below each other, has been developed for practical use. In addition, a memory card driving device is disclosed in which an upper and a lower driving device are assembled together using an assembly leg, while a two-tier memory card driving device is loaded on a printed circuit board (for example, Japanese Unexamined Patent Application Publication No. H7-302645, hereinafter referred to as Patent Document 1).
In the two-tier memory card driving device, in a case where a card connector, in which cards and ejection buttons are oriented in the same direction and which can be loaded on both surfaces of a printed circuit board, is to be realized, it has been difficult to make a common housing due to a coupled structure of a housing and a cover.
In a card connector, in which cards and ejection buttons are oriented in the same direction and which can be loaded on both surfaces of a printed circuit board, if a coupled structure of housing and cover can be constructed such that the housing and the cover are common components, components having different shapes can be reduced, thereby contributing to a reduction of production cost. The above is a problem to be solved by the present invention.


An apparatus for guiding a span of high-speed magnetic recording tape past a recording/transducing head. Low volume pressurized air is utilized to lift the tape off of the guide assembly thereby eliminating sliding friction between the apparatus and the tape. The periphery of the guide is provided with a means to facilitate the formation of an air seal with the edges of the tape thereby substantially isolating the pressurized air from the atmosphere. Air jets are provided at the tangent points where the tape enters and departs from the air guide so as to prevent the tape from touching any portion of the guide during the transport operation. The pressurized air emitted from the air jets located at the tangent point where the tape enters the guide forms a supporting boundary layer of air along the surface of the tape which is carried along by the tape across the guide.

Although many variations of high speed recording tape guides, including air guides, are known and used in the magnetic recording industry, it has been found that a number of serious problems relating to friction and tape alignment have been associated with their use. These problems become particularly acute when processing video signals due to the high tape speeds involved and, consequently, the multiplicity of tracks of extremely narrow width that must be utilized in order to provide record and/or playback capability for programs of reasonable duration on a tape of manageable length.
For example, in a video system which operates at a tape speed of 120 inches per second, 36,000 feet of tape pass the transducing head each hour. Due to physical and cost limitations in reel size, the data is generally recorded on a multiplicity of parallel tracks, and the shorter length of tape which results is passed repeatedly past the transducer head, each time reading information from a different track. In this manner an 1800 foot reel of tape having 30 tracks can be used to record or playback a 90 minute program utilizing the above-described system.
However, the requirement that the tape pass through the transport 30 times per program has resulted in serious wear considerations which it has been found may be greatly overcome through utilization of an air guide type of tape transport. Such prior guides utilizing a film of air as a lubricant have had serious disadvantages associated therewith such as unequal air pressure distribution across the width of the tape which resulted in undesirable deformation of the tape and the requirement for relatively large quantities of air flow under high pressure in order to support the guided span of tape. These problems were eliminated by the air guide designed in accordance with the invention disclosed in my prior U.S. Pat. No. 3,979,037, the disclosure of which is incorporated herein by reference.
Likewise, due to the requirement that 30 different informational tracks be placed in parallel relation on a tape of reasonable and economical width for consumer use, typically 1/4 inch, a related problem concerning alignment of the extremely narrow tracks on the tape with a corresponding transducer head has arisen. This problem is compounded by the fact that commercially available magnetic tape is manufactured to width tolerances which approach the individual track width required (typically about 6 mil with 2 mil spacing between tracks) for utilization of 30 tracks on a 1/4 inch tape format. Such alignment problems have been solved by the air guide designed in accordance with the invention disclosed in my prior U.S. Pat. No. 4,071,177, the disclosure of which is also incorporated herein by reference.
Although the above-discussed prior inventions provided acceptable results in many high-speed tape transport systems, it has been found that due to the fact that the tape must come into contact with the tape guide at the tangent points where the tape enters and departs from the air guide so as to provide an adequate air seal, both undesirable amounts of scrape flutter and contamination build-up on the guide surfaces at these points has resulted which degrade the overall performance of the video system.

Air guide for tape transports having air jets at tangent points


An unmanned aerial vehicle (UAV) that includes a light and a cooling system is described. The light fitted to the UAV may be bright since heat it generates will be cooled by thermal conduction, convection and/or heat absorption. The light may be cooled by the airflow generated by the propellers. The cooling system of the lighted UAV may include radiator that may conduct heat to the environment and/or include an internal liquid cooling system. The cooling system may include dedicated fans to cool the lights.

In recent years, UAVs have been developed and put into use in different applications. Besides UAVs such as large drones used in military applications, smaller consumer-level UAVs have recently become more popular in civilian applications due to their ease of use. For example, smaller self-stabilizing UAVs are now commonly used by aviation enthusiasts with little or no flight training, similar to how small-scale airplanes and helicopters have been used by skilled hobbyists for some time.
More recently, UAVs have been used as display items, to carry objects and serve other functions. For example, UAVs have been fitted with lights and flown in formation under computer control by the Austrian group Ars Electronica in 2012 to provide a visual display where the positions of the lights may be varied. As another example, U.S. Publication No. 2014/0236388 by Disney Enterprises, discloses the use of lighted UAVs that fly under computer control. In this application, the lighted UAVs are referred to as flying lanterns or flying pixels (flixels).
However, the amount of light provided by the foregoing and other current lighted UAVs is significantly limited. For example, current lighted UAVs are generally fitted with lights that do not provide significant lumens. This is a significant problem where, for example, the UAV is intended to fly high above the ground or otherwise viewed from a great distance. In this situation, because the light fitted to the UAV does not provide significant lumens, it may not be readily visible to observers on the ground. As another example, if the lighted UAV is operated in an area where there other lighting exists nearby, the light on the UAV may be drowned out or otherwise non-discernible to observers on the ground due to such "light pollution." As yet another example, where the UAV is flying in daylight, low power lighting used with current UAVs could be imperceptible.
A reason why current lighted UAVs are fitted with low power lighting is because they cannot accommodate the heat generated by high-power lights. For example, LED lights that provide significant lumens also generate significant heat, and none of the above-referenced lighted UAVs address heat issues associated with such powerful LEDs.
Furthermore, simply fitting high-lumen lights to existing UAVs without cooling mechanisms presents other significant heating issues. For example, many high-lumen LED lights would overheat in a very short time, thereby preventing any type of sustained display time. In reality, such high-lumen LEDs could create a fire in a short amount of time if not cooled. In this case, even one minute flight display times are not possible, and such heat could disable the aircraft and cause a safety hazard to viewers. In any event, requiring a UAV to land after a very short flight time to avoid overheating the light or heat damage to the UAV severely limits the manners in which the UAV may be used.
Beyond cooling issues existing with high-lumen lights, the UAV may include other components such as electrical circuits, motors, and the like that generate heat and that may fail without cooling if the UAV operates those devices for extended periods. The above-referenced lighted UAVs do not address this issue.
Accordingly, there is a need for a UAV with a high-lumen lighting system so that the lighting display seen from distances, is not drowned out by nearby light pollution and/or may be visible during daylight hours. There is also a need for a UAV with a cooling system that may cool high-lumen lighting and other heat-generating components to avoid damage or other heat generated problems.

Unmanned aerial vehicle with lighting and cooling therefor


An internal combustion engine comprising an engine block having two opposed guide slots on an interior surface. The guide slots may be parallel to the direction of movement of the engine pistons. At least one pair of cylinders may be formed in the engine block. The pistons may each be moving in a linear direction perpendicular to the inside of a respective one of the cylinders in response to energy forces in a respective chamber positioned at one end of each cylinder.

Internal combustion engines are used in a wide variety of applications relating to transportation, generation of electricity and other industrial applications. A chamber is generally filled with a combustible gas which is ignited causing a piston to move inside a cylinder in a direction outward from the direction of the ignition.
A connecting rod is generally used to transfer the energy from the piston to a crankshaft. The crankshaft is then used to perform work such as turning an electrical generator or driving the wheels of an automobile. As the crankshaft turns, the piston oscillates between two positions. As a result, the connecting rods generally move from side to side about the rotation of the driveshaft. This side to side motion causes stresses in the cylinder, the piston and between the piston rings and the cylinder wall.
To compensate for these stresses, previous approaches have extended the height of the piston in order to provide greater surface area contact between the piston and the cylinder wall. As a result, the side to side forces are reduced, but at the expense of greater friction and additional wear upon the piston rings.
Certain previous approach engines, such as U.S. Pat. No. 5,435,232, have shown a single piston connected to two or more connecting rods. However, such an arrangement does not provide the benefits of the present invention, such as reducing the side to side forces, reducing friction and reducing additional wear upon the piston rings. Other such previous approaches are generally limited to a single piston driving one or more connecting rods.


Disclosed is a test socket for inspecting an electronic device that is particular about properties.

A semiconductor chip is formed with a fine electronic circuit by high-density integration, and during a fabrication process, each electronic circuit undergoes a test on whether it operates normally or abnormally.
For the test on the semiconductor chip, a contact probe, which electrically connects a terminal of the semiconductor chip and a contact point (pad) of an inspection circuit board for applying a test signal, has been used for semiconductor inspection. In general, the semiconductor chip includes terminals arranged having a very fine pattern. Thus, to perform the inspection by contact with the terminals having the very fine pattern, the contact probe needs to have a very fine size to be integrated and supported on a probe supporter.
Further, to minimize loss caused in the test of the test socket for inspecting the semiconductor chip particular about properties, the contact probe needs to have a short length to make a short signal path. However, if the contact probe has the short length, it is difficult to give the contact probe the elasticity enough to absorb pressure applied for the test.
To solve such problems, Korean Patent No. 10-1193556 has disclosed that a printed circuit board mounted with electronic parts and a test socket are integrated. Such a conventional test socket has a structure that a plurality of through holes are arranged in a printed circuit board, and an inner wall of each through hole is coated with a conductive film, and a contact probe (i.e. a conductive rubber) is placed in the through hole and connected to an electric part of the printed circuit board.
However, the conventional test socket is difficult to be used for inspecting a subject having a fine pitch since it has a structure that the contact probe (i.e. a conductive rubber), the electronic parts and a conductive path are formed in a single substrate.
Further, it is very complicated to design the test socket, and thus a production cost increases.

Abstract: The test socket for inspecting electric properties of a subject includes a plurality of probes configured to be retractable in an inspection direction; a probe supporter configured to support the plurality of probes so that first ends of the plurality of probes protrudes to contact with an object contact point of a subject; and a printed circuit board (PCB) configured to be placed beneath the probe supporter, be mounted with electronic parts, be formed with holes through which second ends of the plurality of probes pass, include at least one first pad with which at least one second end of the plurality of probes comes into contact and at least one second pad formed on an opposite side to the first pad, and be formed with electric paths extended from the first pad and the second pad and connected to the mounted electronic parts.