6-Phenyl-Pyrazolopyrimidines of formula I

The present Invention relates to pyrazolopyrimidines of formula I
in which
R1 is C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C2-C10-alkadienyl, or C1-C10-haloalkyl,
xe2x80x83where these radicals may be unsubstituted or partially or fully halogenated or may carry one to three groups Ra,
Ra 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, C2-C6-alkenyloxy, C3-C6-alkynyloxy and C1-C4-alkylenedioxy, which may be halogenated;
xe2x80x83C3-C8-cycloalkyl, C5-C10-bicycloalkyl, phenyl, naphthyl, or 5- or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or
xe2x80x835- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom,
xe2x80x83where the cyclic systems may be partially or fully halogenated or may carry one to three groups Rb:
Rb is halogen, cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, where the alkyl groups in these radicals contain 1 to 6 carbon atoms and the abovementioned alkenyl or alkynyl groups in these radicals contain 2 to 8 carbon atoms;
Y is oxygen, sulfur, NR2 or a single bond; wherein
R2 represents a hydrogen atom or C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C2-C10-alkadienyl, C1-C10-haloalkyl, C3-C8-cycloalkyl, C5-C10-bicycloalkyl, phenyl, naphthyl, or 5- or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or 5- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, where R2 may be substituted by one or more Ra, or
R1 and R2 together with the interjacent nitrogen atom represent a 5- or 6-membered heterocyclic ring, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, which may be substituted by one or more Rc radicals;
m is 0 or an integer from 1 to 4;
L each independently is halogen, nitro, C1-C10-alkyl, C1-C10-alkoxy, and
X is halogen.
Moreover, the invention relates to processes for preparing these compounds, to compositions comprising them and to their use for controlling phytopathogenic fungi.
U.S. Pat. No. 4,567,263 discloses pyrazolopyrimidines which are substituted in the 7-Position by an unsubstituted amino group. These compounds are said to be active against various phytopathogenic fungi.
International Patent Application WO-A 96/35690 embraces pyrazolopyrimidines, to which a substituted phenyl is attached in the 2-position by a phenyl optionally via a linking group.
U.S. Pat. No. 5,817,663 discloses pyrazolopyrimidines, which are substituted by a pentafluorophenyl group in the 6-Position.
However, none of these documents discloses specifically 5-halopyrazolopyrimidines which are substituted in the 6-Position by a phenyl group having up to 4 substituents.
It is an object of the present invention to provide compounds having improved fungicidal activity.
We have found that this object is achieved by the compounds defined at the outset. Furthermore, we have found processes for their preparation, compositions comprising them and methods for controlling phytopathogenic fungi using the compounds I.
The present Invention further provides a process for the preparation of compounds of formula I as defined above which comprises treating a compound of formula IV
in which L, m and X are as defined in formula I; with an alcohol, amine or thiol of formula V
R1xe2x80x94Yxe2x80x94Mxe2x80x83xe2x80x83V
in which R1 and Y are as defined in formula I, and M represents a hydrogen atom or a free or complexed metal atom, to produce compounds of formula I.
For the preparation of the compounds wherein Y represents O, S or NR2, M is preferably a hydrogen atom or a alkali metal.
For the preparation of the compounds wherein Y represents a single bond, M represents a free or complexed metal atom, such as for example Li, Mg or Zn in the presence of a transition metal, in particular Cu.
Compounds of formula IV are novel and can be prepared by reacting 5-amino-pyrazole with 2-phenyl-substituted malonic acid ester of formula II,
wherein L and m are as defined for formula I, R represents alkyl, preferably C1-C6-alkyl, in particular methyl or ethyl, under alkaline conditions, preferably using high boiling tertiary amines as for example tri-n-butylamine as disclosed for example by EP-A 770615.
The resulting 5,7-dihydroxy-6-phenyl-pyrazolopyrimidine of formula III
wherein L and m are as defined for formula I, is subsequently treated with a halogenating agent, preferably with a brominating or chlorinating agent, such as phosphorus oxybromide or phosphorus oxychloride, neat or in the presence of a solvent to give IV.
If phosphorus oxybromide or phosphorus oxychloride is used for the halogenation of III the presence of a mineralic acid, such as polyphosphoric acid, and pyridinium salts, preferably pyridinium halides, such as pyridinium bromide or chloride, is preferred.
The reaction is suitably carried out at a temperature in the range from 0xc2x0 C. to 150xc2x0 C., the preferred reaction temperature being from 80xc2x0 C. to 125xc2x0 C. as disclosed for example by EP-A 770 615.
The compounds of formula II are preferably prepared by reaction of the corresponding substituted bromobenzenes with sodium dialkylmalonates in the presence of a copper(I) salt, [e.g. Chemistry Letters, pp. 367-370, 1981].
Compounds of formula IVA are particularly preferred.
Accordingly, the Invention relates to the novel intermediates of formula IV, in particular 5,7-dichloro-6-(2,4,6-trifluorophenyl)pyrazolo[1,5-xcex1]pyrimidine and 5,7-dichloro-6-(2-chloro-6-fluoro-phenyl)pyrazolo[1,5-xcex1]pyrimidine, and to the corresponding 5,7-dihydroxy-6-phenyl-pyrazolo[1,5-xcex1]pyrimidines of formula III.
The reaction between the 5,7-dihalogen-6-phenyl-pyrazolopyrimidines of formula IV and the compound of formula V, wherein Y is O, S or NR2, is preferably carried out in the presence of an inert solvent.
Suitable solvents include ethers, such as dioxane, diethyl ether and, especially, tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons, for example toluene.
The reaction is suitably carried out at a temperature in the range from 0xc2x0 C. to 70xc2x0 C., the preferred reaction temperature being from 10xc2x0 C. to 35xc2x0 C.
It is also preferred that the reaction is carried out in the presence of a base. Suitable bases include tertiary amines, such as triethylamine, and inorganic bases, such as potassium carbonate or sodium carbonate. Alternatively, an excess of the compound of formula V may serve as a base.
The reaction between the 5,7-dihalogen-6-phenyl-pyrazolopyrimidines of formula IV and the compound of formula V, wherein Y represents a single bond, is conveniently carried out in the presence of a solvent.
Suitable solvents include ethers, such as dioxane, diethyl ether and, especially, tetrahydrofuran, hydrocarbons such as hexane, cyclohexane or mineral oil, and aromatic hydrocarbons, for example toluene, or mixtures of these solvents.
The reaction is suitably carried out at a temperature in the range from xe2x88x92100xc2x0 C. to +100xc2x0 C., the preferred reaction temperature being from xe2x88x9280xc2x0 C. to +40xc2x0 C.
It is also preferred that the reaction is carried out in the presence of copper ions, preferably equimolar amounts of copper(I) halides, in particular copper(I) iodide.
Furthermore the compounds of formula I, wherein Y represents a single bond may be prepared by reacting the corresponding alkyl 2-aryl-3-alkyl-3-oxopropionates of formula VI
in which R1, L and m have the meaning given and Rxe2x80x2 represents an optionally substituted alkyl group, preferably C1-C4-alkyl, with 5-amino-pyrazole.
The reaction mixtures are worked up in a customary manner, for example by mixing with water, phase separation and, if required, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are purified or freed from volatile components under reduced pressure and at moderately elevated temperatures. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.
If individual compounds I are not obtainable by the routes described above, they can be prepared by derivatization of other compounds I.
However, if the synthesis yields isomer mixtures, a separation is generally not necessarily required since in some cases the individual isomers can be converted into one another during the preparation for use or upon use (for example under the action of light, acids or bases). Similar conversions may also occur after use, for example in the treatment of plants in the treated plant or in the harmful fungus or animal pest to be controlled.
In the symbol definitions given in the formulae above, collective terms were used which generally represent the following substituents:
halogen: fluorine, chlorine, bromine and iodine, especially bromine, chlorine or fluorine, in particular fluorine or chlorine;
C1-C10-alkyl and the alkyl moieties of alkoxy, alkadienyl, alkylthio, alkylamino or di-alkylamine: saturated, straight-chain or branched hydrocarbon radicals having 1 to 10, preferably 1 to 6 carbon atoms, especially 1 to 4 carbon atoms, specifically methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di-methylpropyl, 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;
C1-C4-alkylene: methylene, ethylene, n-propylene or n-butylene;
C1-C10-haloalkyl and the haloalkyl moieties of C1-C10-haloalkoxy: straight-chain or branched alkyl groups having 1 to 10, preferably 1 to 4 carbon atoms (as mentioned above), where the hydrogen atoms in these groups may be partially or fully 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;
C2-C10-alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 10, preferably 2 to 6 carbon atoms and a double bond in any position, for example 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 and 2-methyl-2-propenyl;
C2-C10-alkynyl: straight-chain or branched hydrocarbon radicals having 2 to 10, preferably 1 to 4 carbon atoms and a triple bond in any position, for example ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl and 1-methyl-2-propynyl;
Cycloalkyl: monocyclic, saturated hydrocarbon groups with 3 to 6, 8, 10 or 12 carbon atoms, preferably C3-C8-cycloalkyl, specifically cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Bicycloalkyl, as used herein with respect to a radical or moiety refers to a bicycloalkyl group having 5 to 10 carbon atoms, preferably 6 to 9 carbon atoms, in particular bicycloheptyl.
Aryl: a mono- to tricyclic aromatic ring system containing 6 to 14 carbon ring members, for example phenyl, naphthyl and anthracenyl;
5- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom:
5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to, four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, for example 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 groups which, in addition to carbon atoms, may contain one to three or one to four nitrogen atoms as ring members, for example 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.
5- or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 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-1-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-hexahydro-triazin-2-yl and 1,2,4-hexahydrotriazin-3-yl;
Optionally by Ra or Rb substituted moieties may be unsubstituted or have from one up to the maximal possible number of substituents. Typically, 0 to 2 substituents are present.
Preferred meanings for Ra and Rb radicals are: halogen, nitro, cyano, hydroxy, C1-C6-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C1-C6 haloalkyl, C3-C6-halocycloalkyl, C1-C6-alkoxy, C1-C6 haloalkoxy, tri-C1-C4-alkylsilyl, phenyl, halo- or dihalo-phenyl or pyridyl.
The Invention especially relates to compounds of the formula I in which any alkyl or haloalkyl part of the groups R1 or R2, which may be straight chained or branched, contains up to 10 carbon atoms, preferably 1 to 9 carbon atoms, more preferably 2 to 6 carbon atoms, any alkenyl or alkynyl part of the substituents R1 or R2 contains up to 10 carbon atoms, preferably 2 to 9 carbon atoms, more preferably 3 to 6 carbon atoms, any cycloalkyl part of the substituents R1 or R2 contains from 3 to 10 carbon atoms, preferably from 3 to 8 carbon atoms, more preferably from 3 to 6 carbon atoms, any bicycloalkyl part of the substituents R1 or R2 contains from 5 to 9 carbon atoms, preferably from 7 to 9 carbon atoms and any aryl part of the substituent R1 or R2 contains 6, 10 or 14 carbon atoms, preferably 6 or 10 carbon atoms. Any alkyl, alkenyl or alkynyl group may be linear or branched.
The Invention especially relates to compounds of the formula I in which R1 represents a straight-chained or branched C1-C10 alkyl, in particular a branched C3-C10-alkyl group, a C3-C8-cycloalkyl, a C5-C9-bicycloalkyl, a C3-C8-cycloalkyl-C1-C6-alkyl, C1-C10-alkoxy-C1-C6-alkyl, a C1-C10-haloalkyl or a phenyl group being optionally substiuted by one to three halogen atoms or C1-C10-alkyl or C1-C10-alkoxy groups.
The particularly preferred embodiments of the intermediates with respect to the variables correspond to those of the radicals X, Y, R1, R2, L and m of formula I.
A preferred alkyl moiety in formula I is ethyl or especially methyl.
A preferred haloalkyl moiety in formula I is 2,2,2-trifluoroethyl or 1,1,1-trifluoroprop-2-yl.
A preferred alkenyl moiety in formula I is allyl or especially 2-methylallyl.
Preferred heterocyclyl moieties in formula I are pyrrolodinyl, pyrazolidinyl, piperidinyl, piperazinyl or morpholin-4-yl.
Preferred heteroaryl moieties in formula I are: pyridyl, pyrimidyl, pyrazolyl or thienyl.
Cyclic groups in formula I are preferably optionally substituted by one or more halogen atoms, nitro, cyano, C1-C6-alkyl, or C1-C6-alkoxy.
Compounds of formula I are preferred wherein X denotes a fluorine, chlorine or bromine atom, in particular a chlorine atom.
Particular preference is given to compounds of formula I wherein Y represents NR2 or a single bond, in particular NR2.
Moreover, particular preference is given to compounds of formula I in which R2 is hydrogen.
Besides, particular preference is given to compounds of the formula I in which Y denotes NR2 and R2 is hydrogen, C1-C10-alkyl or C1-C10-haloalkyl, in particular hydrogen.
If R1 denotes C1-C10-haloalkyl, preferably a polyfluorinated alkyl group, in particular a 2,2,2-trifluoroethyl, a 2-(1,1,1-trifluoropropyl) or a 2-(1,1,1-trifluorobutyl) group, R2 preferably is hydrogen.
If R1 denotes an optionally substituted C3-C8-cycloalkyl group, preferably a cyclopentyl or cyclohexyl group, R2 preferably is hydrogen or C1-C6-alkyl.
Particular preference is also given to compounds of the formula I in which X is NR2 and R1 and R2 together with the interjacent nitrogen atom form an optionally substituted heterocyclic ring, preferably an optionally substituted C3-C7-heterocyclic ring, in particular a pyrolidine, piperidine, tetra hydropyridine, in particular 1,2,3,6-tetrahydropyridine or azepane ring which is optionally substituted by one or more C1-C6-alkyl, C1-C6-haloalkyl or C1-C6-alkoxy groups, preferably by one C1-C6-alkyl group.
L preferably is halogen or C1-C6-alkoxy. A preferred embodiment are compounds of formula I in which
wherein # denotes the link to the pyrazolopyrimidine moiety, L1 through L4 each independently represent hydrogen, especially fluorine, chlorine, methyl or methoxy, in particular wherein L1 is fluoro, L2 is hydrogen or fluoro, L3 is hydrogen or fluoro or methoxy and L4 denotes hydrogen, fluoro chloro or methyl.
Moreover, particular preference is given to compounds of the formula I in which m is 2 or 3. Most preferred L4 is not hydrogen.
Furthermore, particular preference is given to compounds of formula IA in which the variables have the meaninng as defined in formula I.
Preference is given to compounds of formula IA in which L1 denotes halogen and L3 and L4 each independently represent hydrogen, halogen or C1-C4-alkoxy.
Included in the scope of the present Invention are (R) and (S) isomers of compounds of general formula I having a chiral center and the racemates thereof, and salts, N-Oxides and acid addition compounds.
Particularly preference is given to compounds of formula IA wherein R2 is hydrogen, L1 and L4 independently represent fluorine or chlorine atoms, and L3 denotes hydrogen, fluorine, chlorine or methoxy.
Likewise, preference is given for the following compounds of formula I:
[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-(2,2,2-trifluoro-ethyl)-amine,
[5-chloro-6-(2,4,6-trifluorophenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-cyclopentyl-amine,
[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-(1,1,1-trifluoro-prop-2-yl)-amine,
[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-diethyl-amine,
[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-isopropyl-amine,
sec-butyl-[5-chloro-6-(2,4,6-trifluorophenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl)-amine,
bicyclo[2,2,1]hept-2-yl-[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-amine,
[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]cyclopentyl-amine,
[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-(2,2,2-trifluoro-ethyl)-amine,
[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-(1,1,1-trifluoro-prop-2-yl)-amine,
[5-chloro-6-(2-chloro-6-fluoro-phenyl)pyrazolo[1,5-xcex1]pyrimidin-7-yl]-diethyl-amine,
[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-isopropyl-amine,
sec-butyl-[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]amine,
bicyclo[2,2,1]hept-2-yl-(5-chloro-6-(2-chloro-6-fluoro-phenyl)pyrazolo[1,5-xcex1]pyrimidin-7-yl]-amine,
[5-chloro-6-(2,6-difluoro-4-methoxyphenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-(2,2,2-trifluoro-ethyl)-amine,
[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-4-methyl-cyclohexane,
[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-4-methyl-cyclohexane, and
[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-4-fluoro-cyclohexane.
Moreover, particular preference is given to following compounds:
[5-chloro-6-(2,4,6-trifluoro-phenyl)-7-(4-methyl-piperidin-1-yl)-1,2,4]triazolo[1,5-xcex1]pyrimidine;
[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-(2,2,2-trifluoro-ethyl)amine;
[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]cyclopentyl-amine;
[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-(1,1,1-trifluoro-prop-2-yl)-amine;
[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-diethylamine;
[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]isopropyl-amine;
sec-butyl-[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-amine;
bicyclo[2,2,1]hept-2-yl-[5-chloro-6-(2,4,6-trifluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]amine;
[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]cyclopentyl-amine;
[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl](2,2,2-trifluoroethyl)-amine;
[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl](1,1,1-trifluoroprop-2-yl)-amine;
[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]diethyl-amine;
[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]isopropyl-amine;
sec-butyl-[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-amine;
[5-chloro-6-(2,6-difluoro-4-methoxyphenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl](1,1,1-trifluoroprop-2-yl)-amine;
bicyclo[2,2,1]hept-2-yl-[5-chloro-6-(2-chloro-6-fluoro-phenyl)-pyrazolo[1,5-xcex1]pyrimidin-7-yl]-amine.
With respect to their use, particular preference is given to the compounds I compiled in the tables below. The groups mentioned in the table for a substituent are furthermore for their part, independently of the combination in which they are mentioned, a particularly preferred embodiment of the respective substituents.
Table 1
Compounds of the formula IA, in which L1 is fluoro, L3 is hydrogen, L4 is chloro and R1 and R2 correspond to one row in Table A
Table 2
Compounds of the formula IA, in which L1 and L4 each are fluoro, L3 is hydrogen and R1 and R2 correspond to one row in Table A
Table 3
Compounds of the formula IA, in which L1 and L4 each are chloro, L3 is hydrogen and R1 and R2 correspond to one row in Table A
Table 4
Compounds of the formula IA, in which L1 is methyl, L3 is hydrogen, L4 is fluoro and R1 and R2 correspond to one row in Table A
Table 5
Compounds of the formula IA, in which L1, L3 and L4 each are fluoro and R1 and R2 correspond to one row in Table A
Table 6
Compounds of the formula IA, in which L1 and L4 each are fluoro, L3 is methoxy and R1 and R2 correspond to one row in Table A
Due to excellent activity, the compounds of formula I may be used in cultivation of all plants where infection by phytopathogenic fungi is not desired, e.g. cereals, solanaceous crops, vegetables, legumes, apples, vine.
The compounds according to formula I are superior through their valuable fungicidal properties, in particular their enhanced systemicity and enhanced fungicitoxity.
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 tissues) and in the protection of stored products.
The compounds I are applied by treating the fungi, or the plants, seeds, 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 rates of application are from 0.01 to 2.0 kg of active ingredient per ha, depending on the nature of the effect desired.
In the treatment of seed, 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 rate of application of active ingredient depends on the nature of the field of application and on the effect desired. Rates of application conventionally used in the protection of materials are, for example, from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient per cubic meter of material treated.
For example, they can be used in agriculture or related fields for the control of phytopathogenic fungi such as Alternaria solani, Botrytis cinerea, Cercospora arachidicola, Cercospora beticola, Cladosporium herbarum, Cochliobolus miyabeanus, Corticium rolfsii, Erysiphe graminis, Erysiphe cichoracearum und Sphaerotheca fuliginea, Fusarium-species, Erysiphe cichoracearum, Helminthosporium tritici repentis, Leptosphaeria nodorum, Micronectriella nivalis, Monilinia fructigena, Mycosphaerella ligulicola, Mycosphaerella pinodes, Phytophthora infestans, Plasmopara viticola, Pseudocercosporella herpotrichoides, Puccinia-species, Pyricularia oryzae, Rhizoctonia solani, Sclerotinia sclerotiorum, Sphaerotheca fuliginea, Uncinula necator and Venturia inequalis. The compounds of formula I according to the Invention possess a high fungicidal activity within a wide concentration range.
The Invention further provides a fungicidal composition which comprises an active ingredient, which is at least one compound of formula I as defined above, and one or more carriers. A method of making such a composition is also provided which comprises bringing a compound of formula I as defined above into association with the carrier(s). Such a composition may contain a single active ingredient or a mixture of several active ingredients of the present Invention. It is also envisaged that different isomers or mixtures of isomers may have different levels or spectra of activity and thus compositions may comprise individual isomers or mixtures of isomers.
A composition according to the Invention preferably contains from 0.5% to 95% by weight (w/w) of active ingredient.
A carrier in a composition according to the Invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may for example be a plant, seed, soil, or water in which a plant grows, or to facilitate storage, transport or handling. A carrier may be a solid or a liquid, including material which is normally a gas but which has been compressed to form a liquid.
The compositions may be manufactured into e.g. emulsion concentrates, solutions, oil in water emulsions, wettable powders, soluble powders, suspension concentrates, dusts, granules, water dispersible granules, micro-capsules, gels, tablets and other formulation types by well-established procedures. These procedures include intensive mixing and/or milling of the active ingredients with other substances, such as fillers, solvents, solid carriers, surface active compounds (surfactants), and optionally solid and/or liquid auxiliaries and/or adjuvants. The form of application such as spraying, atomizing, dispersing or pouring may be chosen like the compositions according to the desired objectives and the given circumstances.
Solvents may be aromatic hydrocarbons, e.g. Solvesso(copyright)200, substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, e.g. cyclohexane or paraffins, alcohols and glycols as well as their ethers and esters, e.g. ethanol, ethyleneglycol mono- and dimethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, or xcex3-butyrolactone, higher alkyl pyrrolidones, e.g. noctylpyrrolidone or cyclohexylpyrrolidone, epoxidized plant oil esters, e.g. methylated coconut or soybean oil ester and water. Mixtures of different liquids are often suitable
Solid carriers, which may be used for dusts, wettable powders, water dispersible granules, or granules, may be mineral fillers, such as calcite, talc, kaolin, montmorillonite or attapulgite. The physical properties may be improved by addition of highly dispersed silica gel or polymers. Carriers for granules may be porous material, e.g. pumice, kaolin, sepiolite, bentonite; nonsorptive carriers may be calcite or sand. Additionally, a multitude of pre-granulated inorganic or organic materials may be used, such as dolomite or crushed plant residues.
Pesticidal compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amounts of a carrier which is a surfactant facilitates this process of dilution. Thus, preferably at least one carrier in a composition according to the invention is a surfactant. For example, the composition may contain at two or more carriers, at least one of which is a surfactant.
Surfactants may be nonionic, anionic, cationic or zwitterionic substances with good dispersing, emulsifying and wetting properties depending an the nature of the compound according to general formula I to be formulated. Surfactants may also mean mixtures of individual surfactants.
The compositions of the Invention may for example be formulated as wettable powders, water dispersible granules, dusts, granules, tablets, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols.
Wettable powders usually contain 5 to 90% w/w of active ingredient and usually contain in addition to solid inert carrier, 3 to 10% w/w of dispersing and wetting agents and, where necessary, 0 to 10% w/w of stabilizer(s) and/or other additives such as penetrants or stickers. Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and may be diluted in the field with further solid carrier to give a composition usually containing 0.5 to 10% w/w of active ingredient.
Water dispersible granules and granules are usually prepared to have a size between 0.15 mm and 2.0 mm and may be manufactured by a variety of techniques. Generally, these types of granules will contain 0.5 to 90% w/w active ingredient and 0 to 20% w/w of additives such as stabilizer, surfactants, slow release modifiers and binding agents. The so-called xe2x80x9cdry flowablesxe2x80x9d consist of relatively small granules having a relatively high concentration of active ingredient.
Emulsifiable concentrates usually contain, in addition to a solvent or a mixture of solvents, 1 to 80% w/v active ingredient, 2 to 20% w/v emulsifiers and 0 to 20% w/v of other additives such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are usually milled so as to obtain a stable, nonsedimenting flowable product and usually contain 5 to 75% w/v active ingredient, 0.5 to 15% w/v of dispersing agents, 0.1 to 10% w/v of suspending agents such as protective colloids and thixotropic agents, 0 to 10% w/v of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation and crystalization or as antifreeze agents for water.
Aqueous dispersions and emulsions, for example compositions obtained by diluting the formulated product according to the Invention with water, also lie within the scope of the Invention.
Of particular interest in enhancinig the duration of the protective activity of the compounds of this invention is the use of a carrier which will provide slow release of the pesticidal compounds into the environment of a plant which is to be protected.
The biological activity of the active ingredient can also be increased by including an adjuvant in the spray dilution. An adjuvant is defined here as a substance which can increase the biological activity of an active ingredient but is not itself significantly biologically active. The adjuvant can either be included in the formulation as a coformulant or carrier, or can be added to the spray tank together with the formulation containing the active ingredient.
As a commodity the compositions may preferably be in a concentrated form whereas the end user generally employs diluted compositions. The compositions may be diluted to a concentration down to 0.001% of active ingredient. The doses usually are in the range from 0.01 to 10 kg a.i./ha.
Examples of formulations according to the Invention are:
The compositions of this Invention can be applied to the plants or their environment simultaneous with or in succession with other active substances. These other active substances can be either fertilisers, agents which donate trace elements or other preparations which influence plant growth. However, they can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, algicides, molluscicides, rodenticides, virucides, compounds inducing resistance into plants, biological control agents such as viruses, bacteria, nematodes, fungi and other microorganisms, repellents of birds and animals, and plant growth regulators, or mixtures of several of these preparations, if appropriate together with other carrier substances conventionally used in the art of formulation, surfactants or other additives which promote application.
The other fungicidal compound can be, for example, one which is also capable of combating diseases of cereals (e.g. wheat) such as those caused by Erysiphe, Puccinia, Septoria, Gibberella and Helminthosporium spp., seed and soil Borne diseases and downy and powdery mildews on vines, early and late blight an solanaceous crops, and powdery mildew and scab an apples etc. These mixtures of fungicides can have a broader spectrum of activity than the compound of general formula I alone.
Examples of the other fungicidal compounds are anilazine, azoxystrobin, benalaxyl, benomyl, binapacryl, bitertanol, blasticidin S, Bordeaux mixture, bromuconazole, bupirimate, captafol, captan, carbendazim, carboxin, carpropamid, chlorbenzthiazon, chlorothalonil, chlozolinate, copper-containing compounds such as copper oxychloride, and copper sulfate, cycloheximide, cymoxanil, cypofuram, cyproconazole, cyprodinil, dichlofluanid, dichlone, dichloran, diclobutrazol, diclocymet, diclomezine, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, diniconazole, dinocap, ditalimfos, dithianon, dodemorph, dodine, edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole, famoxadone, fenapanil, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin, fentin acetate, fentin hydroxide, ferimzone, fluazinam, fludioxonil, flumetover, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, IKF-916, imazalil, iminoctadine, ipconazole, iprodione, isoprothiolane, iprovalicarb, kasugamycin, KH-7281, kitazin P, kresoxim-methyl, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methfuroxam, MON 65500, myclobutanil, neoasozin, nicket dimethyldithiocarbamate, nitrothalisopropyl, nuarimol, ofurace, organo mercury compounds, oxadixyl, oxycarboxin, penconazole, pencycuron, phenazineoxide, phthalide, picoxystrobin, polyoxin D, polyram, probenazole, prochloraz, procymidione, propamocarb, propiconazole, propineb, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quinomethionate, quinoxyfen, quintozene, spiroxamine, SSF-126, SSF-129, streptomycin, sulfur, tebuconazole, tecloftalame, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tolclofosmethyl, tolylfluanidt triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin A, vinclozolin, XRD-563, zarilamid, zineb, ziram.
In addition, the co-formulations according to the Invention may contain at least one compound of formula I and any of the following classes of biological control agents such as viruses, bacteria, nematodes, fungi, and other microorganisms which are suitable to control insects, weeds or plant diseases or to induce host resistance in the plants. Examples of such biological control agents are: Bacillus thuringiensis, Verticillium lecanxc3xc, Autographics californica NPV, Beauvaria bassiana, Ampelomyces quisqualis, Bacilis subtxc3xcis, Pseudomonas chlororaphis, Pseudomonas fluorescens, Steptomyces griseoviridis and Trichoderma harzianum.
Moreover, the co-formulations according to the Invention may contain at least one compound of formula I and a chemical agent that induces the systemic acquired resistance in plants such as for example isonicotinic acid or derivatives thereof, 2,2-dichloro-3,3-dimethylcyclopropanecarboxylic acid or BION.
The compounds of general formula I can be mixed with soil, pest or other rooting media for the protection of the plants against seed-borne, soil-borne or foliar fungal diseases.
The Invention still further provides the use as a fungicide of a compound of formula I as defined above or a composition as defined above, and a method for combating fungus at a locus, which comprises treating the locus, which may be for example plants subject to or subjected to fungal attack, seeds of such plants or the medium in which such plants are growing or are to be grown, with such a compound or composition.
The present Invention is of wide applicability in the protection of crop and ornamental plants against fungal attack. Typical crops which may be protected include eines, grain crops such as wheat and barley, rice, sugar beet, top fruit, peanuts, potatoes, vegetables and tomatoes. The duration of the protection is normally dependent an the individual compound selected, and also a variety of external factors, such as climate, whose impact is normally mitigated by the use of a suitable formulation.
The following examples further illustrate the present Invention. It should be understood, however, that the Invention is not limited solely to the particular examples given below.

Abstract: wherein

Abstract: R1 is alkyl, alkenyl, alkynyl, alkadienyl or haloalkyl, cycloalkyl, bicycloalkyl, phenyl, naphthyl, or 5- or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or 5- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom,

Abstract: xe2x80x83where these radicals may be unsubstituted or substituted as defined in the specification,

Abstract: Y is oxygen, sulfur, NR2 or a single bond; wherein R2 is defined in the specification; and

Abstract: R1 and R2 together with the interjacent nitrogen atom may represent a 5- or 6-membered heterocyclic ring, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, which may be substituted by one or more Rc radicals;

Abstract: m is 0 or an integer from 1 to 4;

Abstract: L each independently is halogen, nitro, alkyl, alkoxy, and

Abstract: X is halogen;

Abstract: processes and intermediates for preparing these compounds, compositions comprising them and their use for controlling phytopathogenic fungi are described.


Various aspects of the present disclosure provide a semiconductor device, for example comprising a finger print sensor, and a method for manufacturing thereof. Various aspects of the present disclosure may, for example, provide an ultra-slim finger print sensor having a thickness of 500 μm or less that does not include a separate printed circuit board (PCB), and a method for manufacturing thereof.

Present finger print sensor packages and methods for fabrication thereof are inadequate. Further limitations and disadvantages of conventional and traditional approaches will become apparent to one of skill in the art, through comparison of such approaches with various aspects of the present disclosure as set forth in the remainder of the present application with reference to the drawings.
Common reference numerals are used throughout the drawings and the detailed description to indicate the same or similar elements.

Package of finger print sensor and fabricating method thereof


The invention provides advances in the arts with useful and novel driver methods. The invention provides circuit driver and control methods for relatively high-current drivers, usable with relatively low-voltage battery power sources. Preferred embodiments include one or more high series resistance capacitors electrically connected with a power source. A low resistance driver circuit regulates power supplied from the capacitors to the load.

It is sometimes desirable to use components with high current requirements in portable electronic apparatus. Problems arise, however with driving high-current devices using relatively low voltage power supplies, such as common batteries for example. On the one hand, battery voltage must be sufficient to drive the high-current devices. On the other hand, the current requirements may be so high that there is a risk of damaging the batteries. An example is the use of powerful LEDs as flash elements in small cameras. Overall, this is desirable in order to reduce battery drain, reduce cost, and minimize device size compared to xenon flash systems. Commonly available Lithium Ion (Li-Ion) batteries often used in such applications are limited in their voltage capacities, however, and are often incapable of withstanding the high currents required for driving the LEDs. One potential solution to the problem is to use the available batteries for charging capacitors capable of being charged to sufficient voltage levels and then in turn using the capacitors to drive the LEDs. In such instances it would be desirable to use a low-resistance switch to drive the LEDs if not for the following problems. The current has a tendency to change as the capacitors are discharged. The LEDs themselves can have significant processing variation, in turn yielding forward voltage variation. There is also a temperature coefficient associated with the forward voltage drop of the LEDs, which affects the charging performance.
Due to the foregoing and other problems and potential advantages, improved driver methods, particularly LED driver methods, would be useful contributions to the applicable arts.


A trailer hitch is disclosed. Said trailer hitch comprises a first bracket assembly, a second bracket assembly, a coupler assembly, and a jack assembly. Said jack assembly is capable of mechanically adjusting first bracket assembly relative to second bracket assembly. Said coupler assembly is capable of releasably attaching to a hitch on a vehicle.

Said trailer hitch systems can be used as an addition to or as a part of a trailer for adjusting the height and leverage of said trailer while attached to a vehicle. Previous systems for adjusting said trailer hitch systems comprise rudimentary approaches such as unloading and reloading said trailer or removing said trailer from said vehicle to make adjustments.
None of the above inventions and patents, taken either singularly or in combination, is seen to describe the instant disclosure as claimed. Accordingly, an improved system and method for adjusting a trailer hitch system would be advantageous.


A method of verifying optical proximity correction includes the steps of generating first mask pattern data from design data under first condition, generating first corrected pattern data by applying optical proximity correction to the first mask pattern data, generating second mask pattern data from the design data under second condition, generating second corrected pattern data by applying optical proximity correction to the second mask pattern data, and comparing the first corrected pattern data and the second corrected pattern data to check whether the first corrected pattern data and the second corrected pattern data match.

1. Field of the Invention
The present invention generally relates to methods, programs, and systems for verifying mask pattern data processes when generating mask patterns, and particularly relates to a method, program, and system for verifying an optical proximity correction process.
2. Description of the Related Art
In manufacturing of semiconductor devices, the pattern shape of a mask pattern is printed on a wafer by use of an optical transfer apparatus. As the miniaturization of semiconductor devices is further advanced, adjacent patterns may come in contact with each other because of an optical proximity effect. Further, corners of patterns may be rounded, and lines may become thinner and severed. By estimating such pattern deformation, the pattern data is processed such as to cancel or mitigate the deformation, thereby performing a correction process for ensuring that desired pattern shape is properly formed on the wafer. This is referred to as an optical proximity correction process.
The optical proximity correction process generates an aid pattern for mask pattern data in order to attain a desired wafer-transfer image by correcting the pattern on the reticle. Conventional pattern correction methods set rules with respect to the patters for correcting design data, and generate an aid pattern for reticle pattern data based on the rules for generating corrected patterns.
In order to check the pattern correction process as to whether it is satisfactory or unsatisfactory, a corrected pattern is generated for a simple predetermined test pattern. Visual inspection of this corrected pattern may then be carried out to see whether a desired pattern has been obtained. When the data is complex and its size is massive as in the case of an actual product, it is practically impossible to conduct visual inspection of the corrected pattern. Even when tools are used for verification, the results may not match each other, resulting in a large number of discrepancies, which makes the verification difficult.
[Patent Document 1] Japanese Patent Application Publication 2002-107908
Accordingly, there is a need for a verification method that can efficiently check whether optical proximity correction is properly working during the process of generating mask pattern data.

Method and system for efficiently verifying optical proximity correction


An apparatus for manipulating an object includes a substrate, an electrically conductive layer disposed on the substrate, and a porous medium comprising an electrically conductive material. The apparatus also includes a dielectric layer conformally disposed on the porous medium to insulate the porous medium from the object during use. The porosity of the porous medium is about 90% or greater. The adhesive strength of the porous medium is about 1 kPa or lower, and the modulus of the porous medium is about 1 GPa or lower.

In many manufacturing processes, pick-and-place operations are often used in handling parts, components, and products. The most common approach for pick-and-place operations is to use mechanical grippers having multi-fingered robotic hands and vacuum-based systems, also referred to as the grasping approach. However, it is usually challenging to use the same gripper to handle objects having different sizes, shapes, orientations, and brittleness. In addition, mechanical grippers typically involve high precision control of the robotic hand, especially in electronics manufacturing where the products are fabricated and assembled in microscales and nanoscales.
Another approach for pick-and-place operations uses devices with tunable surface adhesion. This approach is attractive for pick-and-place operation in small scale because it can achieve high precision with less complicated control compared to the grippers. Viscoelasticity is usually used to achieve tunable surface adhesion. In this technique, the adhesion of elastomers can be tuned by controlling the contact/detach speed between the device and the target object. Elastomers can also have good mechanical compliance, thereby allowing soft contact with the object without damaging the object surface. However, the rate dependency of adhesion control often limits the operation speed and eventually the production throughput. Moreover, the lowest adhesion of elastomers may still be too high to release objects onto some desired substrates, in which case complicated surface structures or additional chemical treatments are employed to decrease the adhesion.

Nanocomposite surfaces with electrically switchable adhesion


A linear friction welding method capable of accurately controlling a welding temperature and capable of lowering the welding temperature is provided. The present invention is a linear friction welding method comprising: a first step of forming a welded interface by bringing one member into contact with the other member; a second step of repeatedly sliding one member and the other member on the same locus and discharging flash from the welded interface in a state where pressure is applied substantially perpendicularly to the welded interface; and a third step of forming a welded surface by stopping the sliding and setting the pressure to be not less than the yield stress and not more than the tensile strength of one member and/or the other member at a desired welding temperature.

Along with the increase in strength of metal materials such as steel and aluminum alloys, the deterioration of strength at a joint portion which determines mechanical properties of a joint structure has become a serious problem. On the other hand, in recent years, a solid-state welding method in which the maximum reaching temperature during welding does not reach the melting point of the material to be welded and the strength decrease at the welding portion is small as compared with the conventional melt welding has attracted attention, and the practical application is rapidly proceeding.
In particular, linear friction welding (LFW: Lineaer Friction Welding) in which metal members are slid in a linear locus does not require the use of tools as in friction stir welding (FSW: Friction Stir Welding), so that it can be easily applied to high melting point metals, and is expected to be put to practical use in various industries.
However, the welding mechanism of the linear friction welding, the appropriate process control method, and the like are not always clear, and the welding condition for each of the members to be joined is actually optimized based on a large number of preliminary tests, experiences, and the like.
On the other hand, for example, Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2015-164738) discloses a friction welding device in which one member is repeatedly moved relative to the other member on the same trajectory while contacting the other member, and the one member is friction joined to the other member, wherein the friction welding device comprises stop means for stopping the relative movement of the one member with respect to the other member during a period from the generation of the stop command to the relative movement of the one member with respect to the other member until the one member moves the trajectory relative to the other member once in accordance with the stop command.
In the friction welding device described in Patent Document 1, when friction welding is performed by repeatedly moving one member in contact with the other member on the same trajectory and by friction welding, if a stop command for relative movement is generated at which timing, it is possible to easily specify whether the relative movement of the two members is just stopped at the timing at which the two members are in the appropriate welding state.


A computing device within a reflective memory system includes a memory block and a special purpose processor. The memory block includes a plurality of memory areas, which are configured to store data of a corresponding one of a plurality of external devices. The special purpose processor is configured to intercept a write request. The write request is associated with a first external device of the plurality of external devices, and the first external device is associated with a first memory area of the plurality of memory areas. The special purpose processor is configured to determine whether the write request is valid or invalid, write the data of the first external device to the first memory area if the write request is valid, and prevent the data of the first external device from being written to the memory block if the write request is invalid.

The subject matter disclosed herein relates to reflective memory systems, and more particularly, protection methods and systems for reflective memory systems.
Reflective memory systems may be used for a variety of distributed simulation and industrial control applications. A reflective memory system is a network of computing devices, where each computing device includes a shared memory block and an up-to-date local copy of the shared data. The shared memory block may be one or more areas of a memory device that can be accessed by the computing devices within the reflective memory system. For example, a first computing device in a reflective memory system may write data to its local shared memory block, which is then written to the shared memory block of a second computing device in the reflective memory system. Additionally, the computing devices within a reflective memory system may read or otherwise access the data stored in the shared memory block of other computing devices within the reflective memory system. The physical and/or logical structure of each local shared memory block that is common to each computing device within the reflective memory system may be referred to as a "reflective memory", a "reflective memory area", and the like.
Since each computing device can write to the local shared memory block of other computing devices within the reflective memory system, a computing device could overwrite data received from another computing device thereby corrupting the information in the reflective memory. Typical precautions against data corruption include using software applications to monitor the reflective memory and update the reflective memory if the data within the reflective memory does not match the data within a local shared memory block. However, using software applications to prevent or reduce data corruption may require relatively large amounts of data processing resources and/or network resources. Additionally, such software applications may be subject to common cause failures and/or software malfunctions.
Thus, there exists a demand for a solution allowing an improvement over existing reflective memory protection systems. There is a demand to provide a reflective memory system that alleviates the need for one or more processors to compare a reflective memory versus a local shared memory block. Furthermore, there is a demand for hardware based reflective memory protection systems that provide diverse means of preventing memory corruption and mitigates common cause failures due to software malfunctions.

Systems and methods for protection of reflective memory systems


The optical data recording media is provided on a substrate with a recording layer changing its optical characteristic dependent upon difference in the heat history, or processes of temperature elevation due to laser beam irradiation and the following cooling. The media is composed of layered structure not only varying its own reflectance or transmittance as an integrated media, but also changing the optical phase of the reflected light or transmitted light, when the optical characteristic of the recording layer is changed. In the method of recording, erasing and reproducing data using this optical data recording media, when the variations of the reflectance is to be detected, recording and erasing are effected after temporarily setting the recording layer in a state having a higher reflectance. On the other hand, when the variations of the transmittance is to be detected, recording and erasing are effected after temporarily setting the recording layer in a state having a higher transmittance. The substrate has such guide grooves that the width of either the convex portion between the guide grooves or the concave portion of the guide grooves is smaller than the diameter of the laser beam spot for reproduction.

The present invention relates to an optical data recording media in which optical characteristics of a material vary dependent on differences in the heat history or processes of temperature elevation due to laser beam irradiation and subsequent cooling. In addition, the present invention relates to a method for recording, erasing and reproducing an optical data on the recording media.
Optical disks for recording and reproducing data using laser beams have drawn great attention as portable file memory means having a large storage capacity, and various kinds of optical disks such as of read-only optical disks, write-once optical disks and overwritable optical disks are known. As overwritable types of the disks, phase-change optical disks, exchange-coupled magneto-optical disks and magnetic field modulation magneto-optical disks are known. In these overwritable optical disks, the phase-change optical disk is adapted to record or erase data by changing the optical characteristics caused by the difference of the heat history or process of temperature elevation due to laser beam irradiation and subsequent cooling. In such a phase-change optical disk, data is recorded, or the latest data is written over the previously recorded data, by modulating the energy of the irradiating light beam between two intensity levels respectively corresponding to optically discriminating two states. Here, there are two energy levels of the irradiating light, that is, the higher level and the lower level, and the former corresponds to "recording power" and the latter corresponds to "erasing power". The reading of data is usually effected by detecting variations in transmittance or reflectance between the aforementioned two states.
Meanwhile, most of these optical data recording media tend to be formed on a transparent substrate provided with guide grooves. As shown in FIG. 1, V-shaped guide grooves 6 are formed on a surface of a substrate 1, and wide convex portions 7 are disposed between guide grooves 6. Accordingly, grooves and convex portions are also formed on a recording layer 3 formed on substrate 1. Hereinafter, for convenience, a substrate having V-shaped guide grooves 6 as shown in FIG. 1 will be referred to as "V-groove substrate."
In a phase-change type optical disk, reproduction signals are regenerated by detecting variations in the reflectance or transmittance consequent upon the physical phase changes. In such a case, the amplitude of reproduction signals becomes larger as the size of recorded marks becomes greater. And the amplitude of the reproduction signals saturates when the size of the recorded marks is equivalent to, or larger than, the beam size of a laser beam spot 10 used for reproduction. For this reason, sufficient amplitude of reproduction signals cannot be obtained unless a recording mark is large as compared to the beam size of the reproduction laser. Nevertheless, since recording marks in practice are small compared to the beam size of the reproduction laser, signals obtained cannot always exhibit sufficient amplitude. Such deterioration of the amplitude of the reproduction signals is more notable as the size of the recording mark becomes smaller because of the recording frequency becomes higher. This also makes it difficult to improve the recording density of phase-change type optical disks.
In order to obtain reproduction signals having a large amplitude, it is possible to optimally design the media structure such that the change in reflectance due to the phase transition may be enhanced. But this also increases the change of the absorptance and causes another problem. That is, upon overwriting operation, signals to be overwritten are apt to be modulated under affection of the prior signals or data, so that the performance of the overwriting operation is degraded.
On the other hand, in order to improve the recording density, Japanese Patent Laid-Open Application (KOKAI) Nos. 2-73537 and 2-113451 disclose methods of providing reproduction signals having sufficient amplitude even for small recording marks. That is, in these methods, the layers structure of the recording media is determined so that the change in reflectance may be small and an optical phase change or difference of the reflected light may be nearly equal to (1.+-.2n).pi.. Such a material having small change in reflectance but causing a large phase difference, however, has a strong dependence of its optical characteristics upon the thickness of each layer of the media, and this requires that the thickness of the layers be within very tight tolerances.

Method for recording, erasing and reproducing data on an optical data recording medium


Methods and systems are provided for purging condensate from a charge air cooler to an engine intake. During an engine deceleration event, airflow through a charge air cooler is temporarily increased to purge stored condensate to the engine intake. By delivering condensate while an engine is not fueled, misfire events resulting from ingestion of water are reduced.

Engines may increase output power by using boosting devices that compress intake air. Since charge compression increases air temperature, charge air coolers may be utilized downstream of a compressor to cool the compressed air, further increasing the potential power output of the engine. As intake air passes through the charge air cooler and is cooled below a dew point, condensation occurs. The condensate may be accumulated at a trap and delivered to the engine subsequently, e.g., during steady-state or cruise conditions, at a controlled rate of ingestion. However, because the ingested water slows the rate of combustion, even small errors in the introduction of water into the engine can increase the likelihood of misfire events. Engine control systems may employ various misfire control approaches to reduce misfires causes by the ingestion of water.
One example approach for addressing moisture induced misfires is shown by Tonetti et al. in EP 1607606. Therein, an intake air flow rate is adjusted based on an oxygen concentration of recirculated exhaust gas to compensate for condensate in the EGR. Another example approach is shown by Wong et al. in U.S. Pat. No. 6,748,475. Therein, a fuel injection and spark timing is adjusted based on a parameter indicative of an oxygen concentration or water concentration of recirculated exhaust gas. This allows misfire events arising during steady-state conditions due to a sudden ingestion of too much water or condensate to be reduced. Even when the amount of water ingested is small, during a transient tip-in from steady state conditions, such as when going from low to moderate air mass flow rates to high air mass flow rates, the ingested water can cause slow combustion issues. In particular, the high mass flow rate can break the surface tension of the condensate, and release from the charge air cooler where the engine ingests it in larger quantities.
However the inventors herein have identified potential issues with such an approach. As one example, even with adjustments to intake air flow rate, fuel injection, and/or spark timing, misfires caused due to condensate ingestion during steady-state conditions may not be sufficiently addressed. Specifically, engine combustion stability during steady-state conditions may be very sensitive to the amount of condensate. Consequently, even small errors in condensate metering can lead to misfires.
In one example, some of the above issues may be addressed by a method for a boosted engine comprising: increasing airflow through a charge air cooler in response to a deceleration event. In this way, condensate can be purged without incurring misfire events.
As one example, an engine controller may deliver condensate collected at a charge air cooler to an engine during a deceleration event. For example, in response to a tip-out, when the engine is spinning un-fueled (e.g., during a deceleration fuel shut off or DFSO event), a valve coupled to the charge air cooler (or coupled between the charge air cooler and the intake manifold) may be opened so that the condensate can be introduced into the engine's intake manifold. Additionally or optionally, an intake throttle may be opened to increase airflow to the engine. By opening the valve and/or throttle during the deceleration, intake manifold vacuum generated from the spinning engine may be advantageously used to draw in the condensate. Additionally the engine could be downshifted to a lower gear, further increasing engine speed (and air mass flow rate), thereby creating additional vacuum force to evacuate the condensate.
A timing of opening the valve and/or throttle may be coordinated with a timing of the deceleration event such that the valve is opened at the same time as cylinder fueling is shut off The valve and/or throttle may then be closed when sufficient condensate has been purged or when cylinder fueling is resumed (e.g., during a tip-in following the tip-out). In this way, by delivering condensate from a charge air cooler to an engine during a deceleration event, the large amount of intake manifold vacuum generated from the engine braking can be advantageously used to draw condensate into the engine. By delivering the condensate to the engine during conditions when cylinder combustion is not occurring, the condensate can pass through the engine system without degrading combustion stability. Further, since the condensate is introduced while no combustion is occurring, concurrent engine actuator adjustments for misfire control may not be required. Overall, a larger amount of condensate may be purged into the engine without increasing engine misfires.
It should be understood that the summary above is provided to introduce in simplified form a selection of concepts that are further described in the detailed description. It is not meant to identify key or essential features of the claimed subject matter, the scope of which is defined uniquely by the claims that follow the detailed description. Furthermore, the claimed subject matter is not limited to implementations that solve any disadvantages noted above or in any part of this disclosure.


An active acoustic meta material system with micro-perforated sheets embedded between porous layers and air gaps, around the output region in front of a speaker, perpendicular to the direction of wave propagation of the sound is disclosed. Sound input is split into two frequency ranges by an active controller, such that a higher frequency range is sent to a traditional speaker which outputs sound via a diaphragm which vibrates in response to electromagnetic signals generated based on the sound input. The sound waves in the lower frequency range are sent to piezoelectric or other type of motion-creating transducers which are mounted to an outer housing or casing containing a plurality of meta material sheets with insulative layers between each meta material sheet. The combination of meta material sheets and insulation layers are calibrated to focus and amplify the vibrational waves which are outputted by the transducers.

Loudspeakers or speakers covert an electrical impulse into a mechanical impulse which produces sound, usually by way of the use of electromagnetism which moves a cone. For purposes of this disclosure, a "loudspeaker" is defined as an electro-acoustic transducer which converts an electrical signal into audio output. Such devices are integral parts of every common audio system. This process involves many difficulties and has proven to be the most problematic of the steps to reproduce sound. As a result, loudspeakers are almost always the limiting element in the fidelity of the acoustics of the reproduced sound in home, theater, or in many entertain systems. The other elements in sound reproduction are mostly electronic which are highly advanced and developed.
Ideally, a loudspeaker should create a sound field proportional to the electric signal of the amplifier. Due to the physics of sound radiation, the output is almost always less than ideal particularly in the low frequency region. In general, the common loudspeaker may be split into two parts: an electromechanical and a mechanical-acoustical part. The latter has a diaphragm, the vibration of which creates sound pressure. One of the greatest difficulties in the conversion of electrical into acoustical energy has been the realization of a prescribed (mostly flat) frequency response in a certain (mostly large, broadband) frequency range. The broadband frequency range, for purposes of this disclosure, is between 20 and 20,000 Hz (Hertz).
An unenclosed loudspeaker radiates sound as an acoustic "dipole". This gives rise to a poor low frequency or bass response since sound from the back of the diaphragm cancels sound from the front. For purposes of this disclosure, low frequency or bass response refers to sound less than 200 Hz, 100 Hz, or 80 Hz. The sound also radiates highly directionally. To avoid these problems, the loudspeaker can be mounted in an infinite baffle, in which case it radiates into the "half space" in front of the baffle as a monopole. Even with infinite baffles, loudspeaker radiation efficiency lessens considerably at low frequencies with a simple baffle board. To deal with this impracticality, the infinite baffle is "folded" around the back of the loudspeaker, forming an 'infinite baffle' enclosure (a closed box). However, this does not solve the problem of poor bass response.
Even with a good enclosure a single loudspeaker can not be expected to deliver optimally balanced sound over the entire audible frequency range. The requirements of producing adequate acoustic output at both low and high frequencies are mutually incompatible. In the high frequency range, the driver needs to be light and small to be able to respond rapidly to applied signal. Such high frequency speakers are known as tweeters. On the other hand, a bass speaker should be large to efficiently match the impedance to air. Such speakers, called, woofers, must also be driven with more power to drive a larger mass. Additionally, due to human ear's low response to bass, more acoustic power must be supplied in the bass or low frequency range. Sometimes, a third, mid-range speaker is also used to achieve a smooth frequency response.
Referring now more specifically to the low frequency response, a subwoofer is a woofer driver used only for the lowest part of the audio frequency range such as below 200 Hz (e.g., consumer systems), below 100 Hz (e.g., professional live sound), or below 80 Hz (as in "THX" approved systems known in the art). Because the intended range of frequencies is limited, subwoofer system design usually has a single driver enclosed in a suitable enclosure. Sound in this frequency range can easily bend around corners by diffraction (as low frequencies are "non-directional"), so the speaker aperture does not have to face the audience, and subwoofers can be mounted in the bottom of the enclosure facing the floor for convenience. To accurately reproduce very low bass notes without unwanted resonances (typically from cabinet panels), subwoofer systems must be solidly constructed and properly braced; good speakers are typically quite heavy. Many subwoofer systems include power amplifiers and electronic sub-filters, with additional controls relevant to low-frequency reproduction. These alternatives are known as "active" or "powered" subwoofers. Active subwoofers, like active monitors, have built-in power amplification to boost low frequency sound. In contrast, "passive" subwoofers require external amplification.
The loudspeaker, which generates acoustic pressure, has an internal source impedance and drives an external load impedance. The ambient air medium is the ultimate coupling load, which presents a low impedance because of its low density. The source impedance of any loudspeaker, on the other hand, is high (compared to the impedance of ambient air), so there will be a considerable mismatch between the source and the load. The result is that most of the energy put into a direct radiating loudspeaker will not be released into the air, but will be converted to heat in the voice coil and mechanical resistances in the unit. The problem is worse at low frequencies where the size of the source is small compared to a wavelength. The source pushes the medium away. At higher frequencies, the radiation from the source is in the form of plane waves that do not spread out. The load, as seen from the driver, is at its highest, and the system is as efficient as it can be.
When the loudspeaker diaphragm vibrates, pressure waves are created in front, which creates the sound we hear. Coupling the motion of the diaphragm to the air properly is difficult due to the very different densities of the vibrating diaphragm and air. This can be viewed as an impedance mismatch. It is known that sound travels better in high density materials than in low density materials, and in a speaker system, the diaphragm is the high density (high impedance) medium and air is the low density (low impedance) medium. The horn assists the solid-air impedance transformation by acting as an intermediate transition medium. In other words, it creates a higher acoustic impedance for the transducer to work into, thus allowing more power to be transferred to the air.
Consumer electronic devices, such as cell phones, tablets, and the like with more features and capabilities are ubiquitous and are positioning to become entertainment centers. However, they also exhibit severe audio deficiencies as mentioned above and pose many additional challenges to maintain the acoustic performance as enclosed acoustic volume size, power and membrane size are reduced significantly. Due to the smaller size of the speaker used in such devices, the low frequency response is severely affected. For example, as the size of the cell phone decreases, the volume of air behind the diaphragm is reduced. This small amount of volume behind the speaker limits the range of motion of the diaphragm. The speaker does not produce enough force to compress the air beyond a certain point, hence causing the air to push back. This reduces the displacement of the speaker diaphragm, which in turn lowers the output. Thus, low frequencies are affected the most by this phenomenon as the diaphragm moves with the largest amount of displacement at these frequencies. Consequently, the frequency response usually rolls off faster at low frequencies (<300 Hz).
A wave can be described as a disturbance that travels through a medium, transporting energy from one location to another location. The medium is simply the material through which the disturbance is moving. In solids, sound waves travel in the form of the vibration or wave of molecules produced when an object moves or vibrates through a medium from one location to another. When an object moves or vibrates, the molecules around the object also vibrate, producing sound. Sound can travel through any medium except vacuum.
Sound fields radiated from loudspeakers can be divided into distinguishable regions. Two of which are the geometrical near field and the far field. Close to the source (the near field), for some fixed angle θ, the sound pressure falls off rapidly, p∝1/r^2. Thus in the near field, the sound pressure level decrease by 12 dB for each doubling of distance r. In the far field, the sound pressure levels decrease monotonically at a rate of 6 dB for each doubling of the distance from the source and are characterized by the criteria given below:r>>λ/(2π),r>>a,r>>πa^2/(2λ),where the inequality represents a factor of 3 or greater, r is distance to the source, a is the characteristic source dimension and λ is the wavelength of radiated sound. Thus, it is advantageous to design loudspeakers according to a far field criterion.
The most commonly used far field reference distance for loudspeaker SPL specifications is 1 meter (or 3.28 feet). Sound field of loudspeakers must be measured at a distance beyond which the shape of the radiation pattern remains unchanged as the changes are caused by path length differences to different points on the surface of the device. For relatively smaller loudspeakers sound field might possibly be measured at 1 meter, but for larger loudspeakers it needs a different far field measurement scheme. For large devices, the beginning of the far-field must be determined, marking the minimum distance at which radiation parameters can be measured. The resultant data can then be referenced back to the 1 meter reference distance using the inverse-square law. This calculated 1 meter response can then be extrapolated to further distances with acceptable error.
Sound-absorbing materials such as foams, fiberglass, absorbent panels, etc. are commonly used in various industries and buildings to reduce noise for which the sound waves are reflected, absorbed and transmitted when they hit a hard surface. A commonly used term to define and evaluate sound absorption is the sound absorption coefficient. The sound absorption coefficient is a measure of the proportion of the sound striking a surface, which is absorbed by that surface, and is usually given for a particular frequency. Thus, a surface which would absorb 100% of the incident sound would have a sound absorption coefficient of 1.00, while a surface which absorbs 35% of the sound, and reflects 65% of it, would have a sound absorption coefficient of 0.35. Materials which are dense and have smooth surfaces, such as glass, have small absorption coefficient, whereas porous-type materials, such as glass wool or fiberglass blankets, that contain networks of interconnected cavities tend to scatter the sound energy and tend to trap it. Therefore, there is greater interaction at the surface of such materials and more opportunities during these scattering reflections for the sound wave to lose energy to the material. Consequently, these materials possess relatively larger sound absorption coefficients in the mid to high frequency range, i.e. above 500 Hz.
A way of increasing the fidelity of acoustic reproduction of sound has long been desired. While sound quality does continue to improve, the efforts in increasing fidelity in far-field applications especially has largely stalled.

Active acoustic meta material loudspeaker system and the process to make the same


The present invention offers a steel-material shearing machine which nips steel materials after self adjusting to an optimum condition and shears all kinds of steel materials. The machine comprises: a supporting frame attached to a mounting bracket so that it can swivel freely; the mounting bracket mounted at the end of the arm of a work machine; a mechanism to hold the supporting frame to the mounting bracket by using a swivel brake mechanism until a swivel force of certain intensity is applied; a lower and upper jaws whose engaging parts are indented on their centers, and which are mounted on the supporting frame by first and second pivots respectively so that they can move freely; a synchronizing pin attached between the upper and lower jaws to operate them with equal angles; fan-shaped patching plates flush mounted on both sides of the upper and lower jaws where they make contact with the supporting frame; adjusting pins with adjustable depth attached on both sides of the supporting frame to press the patching plates; and lining plates attached on the inside of the tip of the lower jaw to guide the tip of the upper jaw.

1. Field of the Invention
This invention relates to a steel-material. shearing machine which is mounted at the end of the arm of work machines such as a power shovel to shear various steel materials.
2. Prior Art
There exist similar kinds of shearing machines, for instance, such as disclosed in the Japanese Patent Public Disclosure [KOKAI] No. 62-271619. As shown in FIG. 12, shearing machines of this kind are equipped with a lower jaw 2 at the end of an arm 1, and an upper jaw 3 is pivoted at the lower jaw 2 by a pivot shaft 4; said upper jaw 3 is operated by a hydraulic cylinder 5 located on the arm 1. The upper jaw 3 is moved against the lower jaw 2 to shear steel materials between the lower jaw 2 and upper jaw 3.
There are other crushing machines for shearing steel materials such as disclosed in the Japanese Patent Public Disclosure [KOKAI] NO 2-232470. A shearing machine of this kind is equipped with a supporting frame 7 to which the centers of a lower jaw 2 and upper jaw 3 are pivoted by shafts 8 as shown in FIG. 13. A hydraulic cylinder 9 is linked to each of the rear end of the lower jaw 2 and upper jaw 3 to nip and shear steel materials between them.
The steel-material shearing machines of the former category cannot change its direction easily since the lower jaw 2 is fixed at the end of the arm 1. In addition, because only the upper jaw 3 is moved, the opening angle is small, and its movement is slow. Furthermore, a large hydraulic cylinder is necessary in order to generate a large force.
The steel-materials shearing machines of the latter category require an inefficient working process because shearing position is fixed, and steel materials must be placed on the right position. In addition, the lower jaw 2 and upper jaw 3 do not cope with twisting. Therefore, shearing may not be completed well because of a gap between the lower jaw 2 and upper jaw 3 due to a large twisting force.


The invention provides a method of operating a communication network and a network itself. The network comprises a plurality of wireless stations, each station being able to transmit and receive data so that the network can transmit a message comprising a plurality of data packets from an originating station to a destination station via at least one intermediate station. At least some of the stations have a controllable antenna system operable to direct a null selectively. The method includes selecting, at each station, one or more probing channels for the transmission of probe signals to other stations. At stations having a controllable antenna system, the presence of interference on said one or more probing channels is detected, and one or more nulls are selectively directed towards the source or sources of the interference. Typically, a null is directed towards a source of interference where the level of the interference exceeds a predetermined level. Each station transmits neighbor gathering probe signals on the selected probing channel or channels, and other stations which receive the neighbor gathering probe signals from a probing station respond directly or indirectly to thereby indicate to the probing station their availability as destination or intermediate neighbor stations. The presence of the nulls affects the ability of other stations to receive the neighbor gathering probe signals, and the resulting variations in the connectivity between stations provides variations in the availability of neighbor stations to each station.

THIS invention relates to a method of operating a multi-station communication network, and to a network as such, of the general kind described in International patent applications nos. WO 96/19887 and WO 98/56140.
Networks of this kind can be utilized commercially, with users being subscribers who are billed for their use of the network. Alternatively, networks of this kind may be utilized by security forces such as police or military forces. A further application for networks of the kind referred to is in Wireless Local Area Networks (WLANs), where a wireless network can be combined with conventional network structures to service fixed and mobile network users. Such networks are usually, but not necessarily, computer networks.
In certain bands, such as the 802.11 standard, the functionality of the network can be compromised by factors such as path loss, the lack of signal penetration, the insufficiency of stations available to serve as intermediary stations and the abundance of various sources of interference.
It is an object of the present invention to provide connectivity possibilities in difficult radio environments, such as in low density, cluttered and/or high interference environments.

Adaptive antenna system for diversity and interference avoidance in a multi-station network


A pipe joint clamp for connecting piping members includes a circular holding portion in which flange portions of the piping members are clamped, and multiple flexion-shaped hinge portions, which protrude from the holding portion toward a diametrically outer side thereof. The hinge portions are resiliently deformable to accommodate a variation of outer diameters of the flange portions. Thus, a protrusion amount of the each hinge portion can be reduced. Accordingly, the space occupied by the clamp at the joint part of the piping members is decreased.

Generally, a clamp is used for connecting piping members, each of which has a flange portion disposed at an end thereof. The clamp is provided with a groove portion which extends in a circumference direction thereof, for example, referring to JP-8-219351A. The flange portions are held in the groove portion to be clamped, so that the piping members are axially fixed to each other.
For example, referring to FIG. 9, a clamp 101 made of a resin includes a circular holding portion 110 for accommodating the flange portions of the piping members, and a flexion-shaped hinge portion 120 which protrudes from the holding portion 110 toward a diametrically outer side thereof.
The hinge portion 120 can be resiliently deformed when the clamp 101 is opened/closed. In this case, the inner diameter of the holding portion 110 is changeable responding to a deformation of the flexion-shaped hinge portion 120, to accommodate the variation of the outer diameters of the flange portions.
However, in the case where the variation of the outer diameters of the flange portions is large, the flexion-shaped hinge portion 120 is to be large-sized to accommodate the variation. Thus, the protrusion amount 'C' of the hinge portion 120 with respect to an outer surface of the holding portion 110 becomes large, so that the space occupied by the clamp 101 at the joint part of the piping members is enlarged.


A driving system for an actuating and sensing module includes an actuating and sensing device and a power supply device. The actuating and sensing device includes a sensor, an actuating device, a microprocessor, and a power controller. The power supply device transfers an energy to the power controller, thereby enabling the sensor and the actuating device.

Nowadays, people pay much attention to the devices and methods of monitoring the air quality in the environment. For example, it is important to monitor carbon monoxide, carbon dioxide, volatile organic compounds (VOC), PM2.5, and so on. The exposure of these gases in the environment will cause human health problems or even harm the life. Therefore, it is important for every country to develop and implement the environmental monitoring technology.
Generally, it is feasible to use an ambient sensor to monitor the air quality in the environment. If the ambient sensor is capable of immediately providing people with the monitored information relating to the environment for caution, it may help people escape or prevent from injuries and influence on human health caused by the gas exposure in the environment. In other words, the ambient sensor is suitably used for monitoring the ambient air in the environment.
Generally, the ambient sensor is used to monitor the environment and provide information about the environment to the user. As known, the monitoring sensitivity and the precision of the ambient sensor should be taken into consideration. If the airflow is transferred to the ambient sensor through natural convection, the amount of the airflow to be received by the ambient sensor is neither stable nor uniform. Under this circumstance, the result of monitoring the environment is usually not accurate. Moreover, since the airflow is transferred to the ambient sensor through natural convection, the response time of the ambient sensor to monitor the ambient sensor is much longer. In other words, the real-time monitoring efficacy is low.
Nowadays, a large-scale environmental monitoring base station is provided to monitor the ambient air quality. However, the large-scale environmental monitoring base station is only suitable for monitoring the ambient air quality in a large area. If the large-scale environmental monitoring base station is used to monitor the air quality in a small area where human activities exist (e.g., the indoor air quality and the ambient air surrounding us), the monitoring result is usually not accurate and can't be acquired quickly. If the sensor is integrated into a portable electronic device, the air quality can be immediately monitored everywhere and at any time. Moreover, the monitored data can be transmitted to a cloud database in real time so as to be constructed and managed. Consequently, the monitored data of the air quality can be accurately and immediately provided. Under this circumstance, an air quality notification mechanism and an air quality processing mechanism are enabled.
Therefore, there is a need of providing a driving system for an actuating and sensing module for increasing the monitoring accuracy of the sensor, increasing the monitoring speed of the sensor, immediately monitoring the air quality everywhere and at any time, transmitting the monitored data to the cloud database to construct and manage the monitored data, and enabling the air quality notification mechanism and the air quality processing mechanism.

Driving system for actuating and sensing module


A control device includes a valve, having a body connected to the first chamber of a cylinder via a first hydraulic connection and to the second chamber of the cylinder via a second hydraulic connection. The control device includes a first hydraulic duct connected to a first actuating-fluid source, and a second hydraulic duct connected to a second actuating-fluid source. The hydraulic ducts communicate with the body of the valve. The valve further includes a distribution device that is movable within the body of the valve, between a first position, in which the distribution device places the first hydraulic connection and the first hydraulic duct in fluid communication, and a second position, in which the distribution device places the second hydraulic connection and the second hydraulic duct in fluid communication.

A hydraulic machine, of the turbine, pump or turbine-pump type generally comprises a runner and a ring gate allowing control over the supply of water to the runner. To do that, the ring gate is able to move between an open position, in which it allows water to pass from a duct supplying the runner, and a closed position in which it closes the duct. The movement of such a ring gate is controlled, in the known way, by a plurality of hydraulic cylinders the rods of which are connected to the ring gate and movements of which are controlled by means of a valve. The movement of the rods in the cylinders therefore causes the movement of the ring gate in the duct supplying the runner. When the pistons of the cylinders, and therefore the rods, move in a first direction, the pistons lift the ring gate toward its open position and when they move in a second direction, the opposite of the first direction, the ring gate is lowered toward its closed position.
It will be readily understood that, for large hydraulic machinery, in which the ring gate is very heavy and bulky, movement toward the closed position requires significantly less force than movement toward the open position during which the ring gate is raised, because of the weight of this ring gate.
It is therefore necessary to supply the cylinders at a higher pressure when the pistons are being moved in the first direction than when they are being moved in the second direction.
The known control devices, which propose to solve this problem by allowing the supply to the cylinders to be switched between a first pressure and a second pressure, are complicated and require the addition of numerous components in addition to the control valve. These components require tricky settings and painstaking maintenance interventions.

Device for controlling the movement of a hydraulic cylinder, particularly for hydraulic machines


Dynamic user training rules can be employed to organize content within a folder. Each folder can be associated with a dynamic rule that defines a number of attribute and weighting factor associations and a folder threshold. Each attribute and weighting factor association can identify an attribute that is common among the contents of the smart folder and associate a weighting factor with the common attribute. Whenever a user manually moves content into or out of the smart folder, the attribute and weighting factor associations and possibly the folder threshold can be updated accordingly, such as by adjusting a value of one or more weighting factors to better reflect how common they are after the content has been manually moved into or out of the folder. In this way, the dynamic rule is automatically updated in response to the user's interaction with the smart folder.

A mailbox is used to store a user's messages. The most common example of a mailbox is an email mailbox used to store emails although mailboxes exist for storing other types of messages or even multiple types of messages. For simplicity, the term email will be used hereafter, including in the claims, to represent not only email by any other type of similar electronic message (e.g., SMS messages, collaboration platform messages, etc.) that is stored in a mailbox.
With the proliferation of email, it has become increasingly difficult to organize a mailbox. One common approach to organizing a mailbox is the use of folders to group together emails. For example, most email services include an inbox folder within the mailbox that groups together the user's received emails. Most email providers also provide folders to group together sent emails, drafts, deleted emails, etc. Such folders are typically default folders having unmodifiable rules defining which emails the folders will contain.
Most email providers also provide the ability to create custom folders within a mailbox. These custom folders may or may not be associated with rules. For example, a user may create a custom folder without rules in which case emails would only be stored in the custom folder if the user manually moved the emails into the custom folder. In contrast, a user may create a custom folder and specify rules defining which emails should be stored in the custom folder. In such cases, the rules can be applied to applicable emails (e.g., to all emails in the mailbox or to emails in a particular folder such as the inbox) to automatically determine whether the emails should be moved into the custom folder. These rules can be applied only at a particular time (e.g., only on emails currently stored in a particular folder) or can be applied on an ongoing basis (e.g., whenever an email is received or sent).
The ability to define custom rules for organizing emails into custom folders facilitates organizing a mailbox. However, defining custom rules that properly organize emails is a tedious, problematic, and difficult process. For these reasons, custom rules are oftentimes only employed by advanced users.

Folders that employ dynamic user training rules to organize content