Agitating device (10) for a digester (1) of a biogas plant (100) having a housing (11) and a driving device (12) for rotatably driving the agitator blades (13-15). The driving device (12) comprises a drive shaft (16) and an electric drive motor (20) wherein the drive motor (20) is accommodated sealed in the housing (11). The drive motor (20) comprises an outer, hollow stator (21) and a rotary rotor (22) which is centrally accommodated therein and is configured at least partially hollow. The rotor (22) is rotatably supported at the housing (11) and comprises a coupling device (23) for non-rotatable coupling with the drive shaft (16) to drive the at least one agitator blade (13-15) by means of the drive shaft (16).

The present invention relates to an agitating device which is in particular but not solely provided for a digester of a biogas plant. Such an agitating device comprises a housing and a driving device for rotatably driving at least one agitator blade of the agitating device. The driving device comprises a drive shaft and a drive motor.
Biogas plants comprise as a rule a digester or a number of digesters into which a substrate is charged to produce biogas. It is necessary to stir or agitate the substrate in the digester interior to obtain and ensure favourable conditions for operating the digester.
Agitators respectively agitating devices are used for stirring, comprising as a rule one or more agitator blade/s for thoroughly mixing the substrate. The prior art has disclosed agitators having a hydraulic drive. These agitators show the advantage that the agitator does not need any electric current for operating within the digester. This is an advantage since the digester interior may contain explosible gas or an explosible gas mixture. However, hydraulic agitators show the drawback that the energy required for operating the agitator needs to be supplied from the outside through hydraulic lines.
Using an agitator having an electric drive motor is simpler in comparison. Although suitable sealing needs to be provided, hydraulic supply lines can be dispensed with. Another drawback of using electric motors is that typical asynchronous motors show a comparatively low rotational force and therefore they are combined with a transmission for operation. This increases the overhead and expenditure and reduces the efficiency degree.

Stirrer unit for a fermenter in a biogas plant


The present disclosure provides an isolated nucleic acid sequence encoding a monomeric photoconvertible fluorescent protein, and fragments and derivatives thereof. Also provided is a method for engineering the nucleic acid sequence, a vector comprising the nucleic acid sequence, a host cell comprising the vector, and use of the vector in a method for expressing the nucleic acid sequence. The present disclosure further provides an isolated nucleic acid, or mimetic or complement thereof, that hybridizes under stringent conditions to the nucleic acid sequence. Additionally, the present provides a monomeric photoconvertible fluorescent protein encoded by the nucleic acid sequence, as well as derivatives, fragments, and homologues thereof. Also provided is an antibody that specifically binds to the photoconvertible fluorescent protein.

In recent years a handful of Aequorea green FP (GFP) homologues cloned from Anthozoan organisms have been reported to undergo irreversible photoconversion from a green fluorescent to a red fluorescent species upon illumination with light of approximately 400 nm. To date, the naturally occurring photoconvertible proteins that have received the most attention are Kaede from coral Trachyphyllia geoffroyi (Ando et al., 2002), EosFP from stony coral Lobophyllia hemprichii (Wiedenmann et al., 2004), and Dendra from octocoral Dendronephthya sp. (Gurskaya et al., 2006). It has also been demonstrated that a non-photoconvertible FP can be engineered to be photoconvertible FPs. Specifically, the photoconvertible FP known as KikGR was engineered from the green fluorescent KikG of the coral Favia favus (Tsutsui et al., 2005).
All green-to-red photoconvertible FPs characterized to date share a common His-Tyr-Gly-derived chromophore structure, and a common photoconversion mechanism (FIG. 1) (Mizuno et al., 2003). The newly synthesized protein first folds into the characteristic beta-barrel structure that defines the Aequorea GFP superfamily (Ormo et al., 1996), and undergoes the steps of post-translational modification that lead to the formation of a green fluorescent chromophore with a conjugated system identical to that of the Aequorea GFP chromophore. The chromophore can exist in either its neutral phenol form or the anionic phenolate form (FIG. 1). Exactly where the equilibrium between these two forms lies is dependent on the local microenvironment of the chromophore (as determined by the amino acid substitutions in close proximity to it) and the pH of the solution. The green-to-red photoconvertible FPs are distinguished from their non-photoconvertible brethren, by the respective consequences of exciting the neutral form which absorbs most strongly at ˜400 nm. In wild-type Aequorea GFP the excited state of the neutral form undergoes excited state proton transfer to form the anionic form, which then emits green fluorescence (Chattoraj et al., 1996). An Aequorea GFP variant that does fluoresce from the neutral form of the excited state has been engineered (Tsutsui et al., 2009). In the case of the green-to-red photoconvertible FPs, excitation of the neutral form leads to a break of the polypeptide chain through the effective beta-elimination of the residue that immediately precedes the chromophore-forming His-Tyr-Gly tripeptide (Mizuno et al., 2003; Tsutsui et al., 2009). This elimination reaction results in the installation of a new double bond between C-alpha and C-beta of the His residue, placing the side chain imidazole into conjugation with the remainder of the avGFP-type chromophore. This extended conjugation decreases the HOMO-LUMO gap and thus shifts the emission into the orange-to-red region of the visible spectrum. Photoconversion via alternate mechanisms has been observed in other color classes of FP (Chudakov et al., 2004; Kremers et al., 2009).
Kaede, the first example of a FP that can undergo an irreversible green-to-red photoconversion upon illumination with UV light, was initially described by Miyawaki and coworkers in 2002 (Ando et al., 2002). Unfortunately, the range of potential applications for Kaede remains limited by the fact that it is an obligate tetramer (Hayashi et al., 2007), and no monomeric variants have been reported. Unlike monomeric FPs, tetrameric FPs are generally detrimental to the proper trafficking and localization of recombinant fusion proteins (Campbell et al., 2002). To produce a monomeric green-to-red photoconvertible FP, the same workers appear to have had more success with engineered variants of the tetrameric KikGR FP which is substantially brighter and more efficiently photoconverted than Kaede (Tsutsui et al., 2005). A monomeric version of KikGR, known as mKikGR, has recently been reported (Habuchi et al., 2008).
The two other green-to-red photoconvertible FPs, EosFP and Dendra (Gurskaya et al., 2006; Wiedenmann et al., 2004), have both been subjected to protein engineering to convert the wild-type tetramers into monomers (Adam et al., 2009; McKinney et al., 2009). However, it is apparent that in both eases the 'monomeric' FP does retain some tendency to form dimers at high concentrations (McKinney et al., 2009). The monomeric variant of EosFP, known as mEos, was created through the introduction of 2 point mutations that disrupted the protein-protein interfaces of the tetrameric species (Nienhaus et al., 2005; Wiedenmann et al., 2004). Expression of mEos temperatures of less than 30 degrees C. is problematic (Wiedenmann et al., 2004), but an effectively monomeric tandem dimer variant does express well at 37 degrees C. (Nienhaus et al., 2006). The problem of poor expression of mEos at 37 degrees C. has been overcome with the engineering of mEos2 (McKinney et al., 2009) through the targeted substitution of residues with solvent exposed side chains. Although mEos2 has been reported to retain some propensity for dimer formation, this property does not appear to have adverse effects on the subcellular targeting of a variety of fusion proteins (McKinney et al., 2009).
As with mEos, Dendra is a monomeric green-to-red photoconvertible FP derived from the wild-type tetrameric DendGFP (Gurskaya et al., 2006). Further optimization of Dendra produced the Dendra2 variant, which is claimed to be brighter and faster maturing (Chudakov et al., 2004). Unlike other members of the class of green-to-red photoconvertible FPs that require UV illumination to promote photoconversion, Dendra can be converted to its red fluorescent state by either cyan or UV wavelengths of light. Although Dendra2 generally behaves as a monomer in relatively dilute solutions, it was observed to reconstitute a protein-protein interface very similar to the typical AC dimer interface observed in crystal structures of tetrameric FPs (Adam et al., 2009). It has been reported that Dendra2 can fluoresce from either the neutral or anionic forms of the photoconverted species.

Allele Biotechnology & Pharmaceuticals, Inc.


A recording/reproducing apparatus records and reproduces, over a partial response channel, a recording signal produced by encoding data according to a convolutional code and reproduces the data from a reproduction signal by iterative decoding using likelihood information. A burst error detector detects a burst error part in the reproduction signal. A substituting part substitutes, for a sampling value included in the burst error part, a predetermined value according to a detected result of the burst error detector.

1. Field of the Invention
The present invention generally relates to data recording/reproducing apparatuses, and more particularly, to a data recording/reproducing apparatus having a substituting part substituting for a burst error and to a method of substituting for a burst error.
2. Description of the Related Art
Apparatuses that record and reproduce data include various recording/reproducing apparatuses, such as recording/reproducing apparatuses of magnetic disks, magnetic tapes, optical disks, magnetic optical disks, and the like. In order to record data on such media, magnetic recording marks are mainly used. It is possible to save data permanently and at lower cost than semiconductor memories by magnetic recording. Nowadays, recording/reproducing apparatuses are essential as information recording apparatuses for computers, for recording such as images and image information having a lot of information.
FIG. 1 shows the construction of a conventional data recording apparatus.
First, a description will be given of a case where data are recorded. User data Uk are input to an encoder 101 that modulates the user data Uk to codes that can be iteratively decoded. Then, data interleaved via a puncture part (MUX puncture) 102 and an interleaver (π) 103 are supplied to an LD driver 104. The LD driver 104 modulates a laser beam based on the supplied data and records the data on an information recording medium 105. In an example shown in FIG. 1, a magnetic optical disk is used as the information recording medium 105 (hereinafter referred to as the "magnetic optical disk 105"). However, a magnetic disk, an optical disk, and other information recording media may also be used. In the case of a magnetic disk, the data are supplied to a magnetic head suitable for the recording medium.
Next, a description will be given of a case where data are reproduced from the magnetic optical disk 105. Recording marks are reproduced from the magnetic optical disk 105 by a head and a MO reproduction signal is obtained. A recording/reproducing system 106 constructed by a writing head, the magnetic optical disk 105, and the reproducing head forms a partial response channel (PR channel) having characteristics such as PR (1, 1). The reproduced MO reproduction signal is amplified by an amplifier 110. Then, the amplitude of the signal is controlled by an AGC 111, and thereafter waveform equalization is performed on the signal by a low-pass filter (LPF) 112 and an equalizer (EQ) 113. The MO reproduction signal Yi subjected to waveform equalization as described above is converted to a digital signal by an A/D converter 114 by using a clock synchronized with the reproduction signal. Then, the digital signal thus converted is accumulated in a memory 115.
Next, based on the data accumulated in the memory 115, the user data are reproduced by a iterative decoder 116 such as a turbo decoder. The iterative decoder 116 is controlled by a controller 117 (for example, an ODC in the case of a magnetic optical disk apparatus). The iterative decoder 116 decodes the user data through iterative decoding of the number of times determined by the controller 117.
FIG. 2 shows an example of the encoder 101 that encodes the user data into codes for performing iterative decoding. The encoder shown in FIG. 2 is an iterative convolutional encoder and is constructed by registers 201 and 202, and exclusive ORs 203 and 204. The encoder shown in FIG. 2 generates a parity sequence pk from the user data sequence Uk.
FIG. 3 shows an example of a conventional construction of the iterative decoder 116 in FIG. 1. Data (a reception signal sequence) yi represent a reception signal digitized by the A/D converter 114 and accumulated in the memory 115 shown in FIG. 1. The sampling data yi are supplied to an a posteriori probability decoder (PR Channel APP) 301. The a posteriori probability decoder 301 calculates, under the condition where input sampling value Y (y1, y2, y3, . . . yn) is detected, a logarithmic likelihood ratio L(ci*) between the probability P (ci=1|y) that the next input bit ci is "1 " and the probability P (ci=0|y) that ci is 0. When iteration is made for the first time, a priori information La(ci) input to the a posteriori probability decoder 301 is all zeros. This represents that the probability that all of the bits ci are "1" and the probability that all of the bits ci are "0" are the same probability (are equal).
Then, the a priori information La(ci) is subtracted from L(ci*), which is the output of the a posteriori probability decoder 301, by a subtractor 302 so as to obtain extrinsic likelihood information Le(c). The extrinsic likelihood information Le(c) is converted by a deinterleaver 303 and thereafter sent to a depuncture part 304. The depuncture part 304 converts the deinterleaved extrinsic likelihood information Le(c) to likelihood information L(uk) corresponding to a data bit Uk and likelihood information L(Pk) corresponding to a parity bit Pk and supplies the information to a code decoder (Code APP) 305. The code decoder 305 outputs a logarithmic likelihood ratio L(u*) with respect to the data bit uk and a logarithmic likelihood ratio L(p*) with respect to the parity bit pk from L(uk) and L(pk), respectively. When performing iterative decoding, L(u*) and L(p*) are sent to a puncture part 306 and converted to likelihood information L(c*)(the result of combining and thinning out L(u*) and L(p*)). A priori information Le(c) is subtracted from L(c*) by a subtractor 307. Then, interleaving is performed by an interleaver 308 on the output of the subtractor 307 so as to obtain La(ci). La(ci) is supplied to the a posteriori probability decoder (PR Channel APP) 301 as a priori information and iteration is repeatedly performed. Data detection is performed such that a hard decision part 309 determines whether L(u*) obtained from the code decoder 305 is "1" or "0" and outputs the user data sequence Uk.
However, the above-described conventional example suffers from the following problems.
Generally, there are local defects in recording media such as optical disks (including magnetic optical disks), magnetic disks, and magnetic tapes. Especially, in optical disks and magnetic tapes that are replaceable media, defective parts are increased by the influence of adhesion of dust and scratches made when handling them. The iterative decoding described above operates very effectively for reduced SNR associated with recording media and apparatuses of higher density. When a reproduction signal (burst error signal) of a defective part in a recording medium is input, however, likelihood information that is made vastly different via a priori information is propagated to data of a part(s) other than the burst error part, and an error in the burst error part is propagated to the data of the other part(s). This is because the likelihood information obtained from the data of the burst error part is greatly different from the likelihood information obtained from the original data. Hence, there is a problem in that the effect of error correction by iterative decoding cannot be obtained sufficiently.

Recording/reproducing apparatus having a substituting part substituting for burst errors and a method of substituting for burst errors


Techniques are described herein that are capable of load-balancing establishment of connections among groups of connector servers in a public computer network by performing operations that include receiving a connection request from a connector client in a private computer network, requesting establishment of a connection between the connector client and one of the connector servers in the public computer network. A number of connections between the private computer network and each group is determined. An identified group is selected from the groups based at least in part on a number of connections between the private computer network and the identified group being less than or equal to a number of connections between the private computer network and each other group. The connection request is provided toward the identified group, which enables establishment of the connection between the connector client and a connector server in the identified group.

A variety of services are available to enable access to private networks through the Internet. Each of the private networks may be an on-premises network or a private cloud. The services typically enable access to the private networks by installing "connector clients" within the private networks. Each connector client that is installed within a private network typically is configured to route traffic from the Internet into the private network. The connector clients traditionally operate generically, listening for incoming resource requests from the Internet.
For example, a connector client may expose a public Internet IP address to receive the resource requests from the Internet, which may require firewall exceptions and network address translation (NAT) rules for traffic to be routed into the connector client within the private network. In another example, the connector client may establish a site-to-site connection to a connector server that is able to access the connector client and the Internet. In this example, the connector server exposes a public internet IP address to receive the resource requests on behalf of the connector client. The site-to-site connection may connect local area networks (LANs) to a joint LAN, and it may not be possible to scale the solution to more than a few connector clients per connector server because the LANs may overlap.
Connector clients in both of the examples mentioned above expose the private networks within which the connector clients are installed to risks by enabling (either directly or via a connector server) creation of a connection from the Internet to a network that is intended to be private and typically behind NAT and a firewall. A connector client traditionally is capable of establishing a site-to-site connection to a single connector server, which may lead to a load of the connector server becoming too great for the connector server to adequately handle. For instance, the burden of the load may cause performance of the connector server to be degraded. Although multiple connector servers may be employed, the use of a load balancer with regard to the connector servers traditionally leads to traffic being routed through the same connector server.

Load-balancing establishment of connections among groups of connector servers


Apparatus and systems, as well as methods and articles, may operate to actively cool an electronic device using a first heat removing cooling element, and to induce a thermal gradient in a heat pipe by conducting heat from a hot side of the first heat removing cooling element to a cold side of a second heat removing cooling element using the heat pipe. The heat pipe may comprise a variable conductance heat pipe. The apparatus and system may operate in a downhole environment, including logging and drilling operations.

Heat storing and heat removing cooling mechanisms have been developed to manage the thermal conditions surrounding thermal components, including electronic devices operating in high temperature locations, such as downhole environments, where temperatures typically reach about 200 C. While heat storing cooling can be effective for a short time, many designers resort to heat removing cooling strategies when extended operating times at high temperatures are anticipated.
Several problems may arise when heat removing cooling elements are used in the downhole environment. For example, single stage elements may be unable to maintain large temperature gradients. Multi-stage elements may not be commercially available. Even if multi-stage elements are used, the heat absorbed by the element (as well as operational heat) may be rejected close to the point of absorption, resulting in convective heat flow back to the object being cooled. For a variety of reasons, then, there is a need to provide improved thermal management solutions for operating electronic devices in downhole environments.


A spray system, which reduces contamination caused by toilet flushing, is activated during a flush cycle to contain waste matter and prevent escape thereof from the bowl. The system is mounted above the level of water in a toilet and includes an aperture that creates a spray and is fluid communication with the flush valve of the toilet. Accordingly, each time the flush valve is activated, a portion of the water provided to the toilet is directed to the aperture to create a spray to minimize escaping effluent.

When toilets are flushed they churn water and that which is contained in the water into the atmosphere near the toilets. Bacteria and viruses from droplets produced by flushing a toilet remain airborne long enough to settle on surfaces throughout a bathroom. These microbes may also float in the air for two hours after each flush.


A running board assembly for a vehicle may include a stationary board fixed to a vehicle body, a movable board separately coupled to the stationary board and selectively movable up and down with respect to the stationary board, a stopper pin selectively coupling the movable board and the stationary board to stop a vertical motion of the movable board to a predetermined position, and a stopper pin-manipulation unit included in the movable board and connected to the stopper pin, wherein when the movable board may be subjected to a load, the stopper pin-manipulation unit decouples magnetically the stopper pin from the stationary board, and wherein when the movable board may be not subjected to the load, the stopper pin-manipulation unit maintains a state of the stopper pin being coupled to the stationary board.

1. Field of the Invention
The present invention relates, in general, to a running board mechanism for a vehicle and, more particularly, to a running board mechanism for a vehicle which is designed to vertically move down and return to its original position.
2. Description of Related Art
Generally, as shown in FIGS. 1A and 1B, a running board 1 aids entry into recreational vehicles (RVs) which have higher ground clearances compared to a sedan.
However, since a conventional running board is simply fixed to a vehicle body 2 (i.e. as a side seal outer panel), there is a drawback in that it is inconvenient for passengers such as the elderly, the disabled and children to step on the running board due to the increased ground clearances and for fear of falling and/or injuring themselves in the process of stepping onto and/or off the running board.
The information disclosed in this Background of the Invention section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art


Novel nitrophenyl-sulphonyl-imidazole of the formula (I)

The present invention relates to novel nitrophenyl-sulphonyl-imidazoles, a process for their prepartion and their use for controlling vegetable and animal pests.
It has already become known that specific phenylsulphonyl-imidazoles and phenylsulphonyl-benzimidazoles have fungicidal properties (cf. EP-A 0 238 824 and WO 97-06 171). Thus, 1-(2-methyl-5-nitro-phenylsulphony)-benzotriazole, 2-menthyl-1-(2-menthyl-5-nitro-phenylsulphony)-imidazole and 1-(2-methyl-5-nitro-phenylsulphonyl)-2-chloro-6,6-difluoro-[1,3]-dioxolo-[4,5-f]-benzimidazole can be used for controlling fungi. The activity of these substances is good but is unsatisfactory in some cases at low application rates.
Novel nitrophenyl-sulphonyl-imidazoles of the formula
in which
a) X represents cyano,
R1 represents halogen, alkyl or phenyl,
R2 represents halogen, alkyl or phenyl or
R1 and R2, together with the carbon atoms to which they are bonded, represent an optionally substituted benzene ring or represent an optionally substituted heterocyclic ring and
R3 represents halogen, alkyl or phenyl or
b) X represents halogen,
R1 represents halogen, alkyl or phenyl,
R2 represents halogen, alkyl or phlenyl or
R1 and R2, together with the carbon atoms to which they are bonded, represent an optionally substituted heterocyclic ring or
R1 and R2, together represent a doubly bonded radical of the formula
xe2x80x83and
R3 represents halogen, alkyl or phenyl,
have now been found.
It has furthermore been found that nitrophenyl-sulphonyl-imidazoles of the formula (I) are obtained if imidazole derivatives of the formula
in which
R1, R2 and X have the abovementioned meanings,
are reacted with nitrobenzene-sulphonyl halides of the formula
in which
R3 has the abovementioned meaning and
Hal represents chlorine or bromine,
optionally in the presence of an acid acceptor and optionally in the presence of a dilueiit.
Finally, it has been found that the nitrophenyl-sulphonyl-imidazoles of the formula (I) are very suitable for controlling vegetable and animal pests in crop protection and in material protection.
Surprisingly, the substances according to the invention exhibit a better fungicidal activity than 1-(2-methyl-5-nitro-phenylsulphonyl)-benzotriazole and 2-methyl-1-(2-methyl-5-nitro-phienylsulphionyl)-imidazole, which are constitutionally similar, previously known active substances having the same type of activity.
The substances according to the invention are generally defined by the formula (I).
A preferred group of substances according to the invention are nitrophenyl-sulphonyl-imidazoles of the formula
Here, the stibstituents preferably have the meanings stated below.
R1 preferably represents fluorine, chlorine, bromine, straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl.
R2 preferably represents fluorine, chlorine, bromine, straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl.
R1 and R2, together with the carbon atoms to which they are bonded, furthermore preferably represent a benzene ring which can be monosubstituted to trisubstituted, identically or differently, by
halogen, cyano, nitro, formyl, carbamoyl, thiocarbamoyl;
alkyl, alkoxy, alkylthio or alkylsulphonyl, each having 1 to 5 carbon atoms;
halogenoalkyl, halogenoalkoxy, halogenoalkylthio or halogenoalkylsulphonyl, each having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms;
halogenioalkenyl or halogenoalkenyloxy, each of which is straight-chain or branched and each of which has 2 to 4 carbon atoms and 1 to 5 identical or different halogen atoms;
alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulphonyloxy, hydrox-iminoalkyl, alkoximinoalkyl or cyanoimino(alkoxy)alkyl, each having 1 to 4 carbon atoms in the individual alkyl moieties;
cycloalkyl having 3 to 6 carbon atoms;
phenyl, phenoxy, phenylthio, pyridyl, pyridyloxy and/or pyridylthio, it being possible for each of these radicals to be monosubstituted or disubstituted, identically or differently, by halogen, cyano, nitro, alkyl having 1 to 4 carbon atoms and/or halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms.
R1 and R2, together with the carbon atoms to which they are bonded, furthermore preferably represent a benzene ring which is substituted by doubly linked alkylene having 3 or 4 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms, it being possible for the alkylene or dioxyalkylene groups to be monosubstituted to tetrasubstituted, identically or differently, by halogen, alkyl having 1 to 4 carbon atoms and/or halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms.
R1 and R2, together with the carbon atoms to which they are bonded, furthermore preferably represent a 5- or 6-membered heterocyclic ring which contains one, two or three identical or different heteroatoms, such as oxygen, sulphur and/or nitrogen, and may be monosubstituted to trisubstituted, identically or differently, by halogen, cyano, nitro, hydroxyl, amino, formyl, carboxyl, carbamoyl, thiocarbamoyl, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, cycloalkyl having 3 to 6 carbon atoms, halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkylamino having 1 to 4 carbon atoms, hydroxyalkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms in each alkyl group, alkylcarbonyl having 1 to 4 carbon atoms in the alkyl moiety, hydroximinoalkyl having 1 to 4 carbon atoms in the alkyl moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, alkylcarbonyloxy having 1 to 4 carbon atoms in the alkyl moiety and/or halogenoalkylcarbonyloxy having 1 to 4 carbon atoms in the halogenoalkyl group and 1 to 5 identical or different halogen atoms, the oxygen atoms not being adjacent where the heterocyclic ring contains more than one oxygen atom.
R3 preferably represents fluorine, chlorine, bromine, straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl.
A further group of preferred substances according to the invention are nitrophenyl-sulphonyl-imidazoles of the formula
In this formula, the substituients preferably have the meanings stated below.
Hal1 preferably represents fluorine, chlorine or bromine.
R1 preferably represents fluorine, chlorine, bromine, straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl.
R2 preferably represents fluorine, chlorine, bromine, straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl.
R1 and R2, together with the carbon atoms to which they are bonded, furthermore preferably represent a 5- or 6-membered heterocyclic ring which contains one, two or three identical or different heteroatoms, such as oxygen, sulphur and/or nitrogen, and may be monosubstituted to trisubstituted, identically or differently, by halogen, cyano, nitro, hydroxyl, amino, formyl, carboxyl, carbamoyl, thiocarbamoyl, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, cycloalkyl having 3 to 6 carbon atoms, halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylsuiphonyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkylamino having 1 to 4 carbon atoms, hydroxyalkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms in each alkyl group, alkylcarbonyl having 1 to 4 carbon atoms in the alkyl moiety, hydroximinoalkyl having 1 to 4 carbon atoms in the alkyl moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, alkylcarbonyloxy having 1 to 4 carbon atoms in the alkyl moiety and/or halogenoalkylcarbonyloxy having 1 to 4 carbon atoms in the halogenoalkyl group having 1 to 5 identical or different halogen atoms, the oxygen atoms not being adjacent where the heterocyclic ring contains more than one oxygen atom
R1 and R2 together furthermore preferably represent a doubly bonded radical of the formula
R3 preferably represents fluorine, chlorine, bromine, straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl.
Particularly preferred are compounds of the formula (Ia), in which
R1 represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl, iso-butyl, tert-butyl or phenyl,
R2 represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or phenyl or
R1 and R2, together with the carbon atoms to which they arc bonded, represent a benzene ring which may be monosubstituted to trisubstituted, identically or differently, by
fluorine, chlorine, bromine, cyano, nitro, formyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methyltillo, ethylthio, n- or i-propylthio, methylsulphonyl, ethylsulphoiiyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethiylthio, trifluoromethylsulphionyl, acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, methylsulphonyloxy, etlylsulphonyloxy, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, ethoximinomethyl, methoximinomethyl, ethoximinoethyl, cyanoimino(methoxy)methyl,
cyclopropyl, cyclopentyl, cyclohexyl or
phenyl, phenoxy, phenylthio, pyridyl, pyridyloxy and/or pyridylthio, it being possible for each of these radicals to be monosubstituted or disubstituted, identically or differently, by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, iso-butyl, tert-butyl, trifluoromethyl, trichloromethyl and/or difluoromethyl, or
R1 and R2, together with the carbon atoms to which they are bonded, represent a benzene ring which is substituted by propane-1,3-diyl, butane-1,4-diyl, methylenedioxy or ethylenedioxy, each of which is doubly linked, it being possible for tile alkylene or dioxyalkylene groups to be monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, trifluoromethyl, methyl, ethyl and/or n-propyl, or
R1 and R2, together with the carbon atoms to which they are bonded, represent a fused furan, thiophene, pyrrole, oxazole, thiazole, imidazole, isoxazole, isothiazole, pyrazole, 1,2,3-oxadiazole, 1,2,3-thiadiazole, 1,2,3-triazole, pyridine, pyridazine, pyrazine, pyrimidine or 1,2,4-triazine ring, it being possible for these radicals to be monosubstituted or disubstituted, identically or differently, by fluorine, chlorine, bromine, cyano, nitro, amino, hydroxyl, formyl, carboxyl, carbamoyl, thiocarbomyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylstilphonlyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthlio, trifluoromethylthio, trifluoromethylsulphinyl or trifluoromethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyloxy, ethylsulphonyloxy, hydroxyiminomethyl, hydroxyiminoethyl, methoxyiminomethyl, ethoxyiminomethyl, methoxyiminoethyl and/or ethoxyiminoethyl and
R3 represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or phenyl.
Particularly preferred in addition are compounds of the formula (Ib), in which
Hal1 represents fluorine, chlorine or bromine,
R1 represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or phenyl,
R2 represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or phenyl, or
R1 and R2, together with the carbon atoms to which they are bonded, represent a fused furan, thiophene, pyrrole, oxazole, thiazole, imidazole, isoxazole, isothiazole, pyrazole, 1,2,3-oxadiazole, 1,2,3-thiadiazole, 1,2,3-triazole, pyridine, pyridazine, pyrazine, pyrimidine or 1,2,4-triazine ring, it being possible for these radicals to be monosubstituted or disubstituted, identically or differently, by fluorine, chlorine, bromine, cyano, nitro, amino, hydroxyl, formyl, carboxyl, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methyltihio, ethylthio, n- or i-propyltliio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difuoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl or trifluoromethylsulplhonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyloxy, ethylsulphonyloxy, hydroxyiminomethyl, hydroxyiminoethyl, methoxyiminomethyl, ethoxyiminomethyl, metlioxyiminoethyl and/or ethoxyiminoethyl, or
R1 and R2 together represent a doubly bonded radical of the formula
xe2x80x83and
R3 represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or phenyl.
The abovementioned meanings of the substituents can be combined with one another in any desired manner. In addition, individual definitions may also be omitted.
The nitrophenyl-sulphonylimidazoles shown in the following tables may be mentioned as examples of substances according to the invention.
If 2,5-dibromo-4-methyl-1H-imidazole and 2-methyl-5-nitrobenzenesulphonyl chloride are used as starting materials, the course of the process according to the invention can be illustrated by the following equation.
The imidazole derivatives required as starting materials for carrying out the process according to the invention are generally defined by the formula (II). In this formula, R1, R2 and X preferably have those meanings which have already been mentioned in connection with the description of the substances, according to the invention, of formula (I) as being preferred for the substituents.
The compounds of the formula (II) may be present in the following two tautomeric forms.
If the molecular unit
is symmetrical, the tautomeric forms are identical. In the reaction, according to the invention, with nitrobenzenesulphonyl halides of the formula (III), only one specific end product of the formula (1) is thus formed in each case, and is formed independently of which of the two tautomeric forms reacts.
If the molecular unit
is asymmetrical, the two tautomeric forms are not identical. In the reaction, according to the invention, with nitrobenzene-sulphonyl halides of the formula (III), end products of the formula (1) which are derived from the tautomeric forms of the formulae (IIa) and/or (IIb) can thus form. If both tautomers react, end products of the formula (I) are obtained in the form of mixtures.
The imidazole derivatives of the formula (II) are known or can be prepared by known methods (cf. WO 97-06171, Chem. Ber. 85, (1952) 1012-1020), J. Med. Chem. 34 (1991), 1110-1116 and J. Chem. Soc. 1965, 3017-3021).
The nitrobenzene-sulphonyl halides furthermore required as starting materials for carrying out the process according to the invention are generally defined by the formula (III). In this formula, R3 preferably has those meanings which have already been mentioned in connection with the description of the substances, according to the invention, of the formula (I) as being preferred for these substituents. Hal also preferably represents chlorine or bromine.
The nitrobenzene-sulphonyl halides of the formula (III) are known or can be prepared by known methods (cf. EP-A 0 238 824).
All customary inorganic or organic bases are suitable as acid acceptors for carrying out the process according to the invention. Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butylate, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate or sodium bicarbonate, furthermore ammonium compounds, such as ammonium hydroxide, ammonium acetate or ammonium carbonate, and tertiary amines, such as triniethiylamiiine, triehliylamine, tributylamine, N,N-dimethylaniilinie, N,N-dimethyl-benlzylaminie, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaniinopyridine, diazobicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU), may preferably be used.
All inert organic solvents are suitable as diluents for carrying out the process according to the invention. Aliphatic, alicyclic or aromatic hydrocarbons such as, for example, petroleum ether, hex ane, heptane, cyclohexane, methylcycloliexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, tetrachloromethane, dichloroethane or tricliloroethane; ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethanie, 1,2-diethoxyethane or anisole; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethyl-phosphorotriamide; esters, such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide; sulphones, such as sulpholane, or amines, such as pyridine, may preferably be used.
When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively large range. In general, temperatures between 0xc2x0 C. and 150xc2x0 C., preferably temperatures between 10xc2x0 C. and 120xc2x0 C., are employed.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to employ superatmospheric or reduced pressure.
When the process according to the invention is carried out, in general 1 to 1.5 mol of nitrobenzene-sulplhonyl halide of the formula (III) and an equivalent amount or an excess of acid acceptor are used per 1 mol of imidazole derivative of the formula (II). The working up is effected by customary methods. In general, water is added to the reaction mixture, the mixture formed is extracted several times with an organic solvent slightly soluble in water, and the combined organic phases are dried and evaporated down. The substances obtained can optionally be purified by customary methods, such as chromatography or recrystallization.
The active substances according to the invention are suitable for controlling vegetable pests and can therefore be used for controlling undesired microorganisms, such as fungi or bacteria, in crop protection and in material protection.
Fungicides can be used in crop protection for controlling plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
Bactericides can be used used in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
Some pathogens of fungal and bacterial diseases which are included under the general terms listed above may be mentioned by way of example without imposing any limitation:
Xanthomonas species, such as Xanthomonas campestris pv. oryzae;
Pseudomonas species, such as Pseudomonas syringae pv. lachryrnans;
Ervinia species, such as Erwinia amylovora;
Pythium species, such as Pythium ultimum;
Phyiophtlora species, such as Phytophthora infestans;
Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperono-spora cubensis;
Plasniopara species, such as Plasmopara viticola;
Bremia species, such as Bremia lactucae;
Peronospora species, such as Peronospora pisi or P. brassicae;
Erysiphe species, such as Erysiphe graminis;
Sphaerotheca species, such as Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotriclia;
Venturia species, such as Venturia inaequalis;
Pyrenophora species, such as Pyrenophora teres or P. graminea (Conidia fonn: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as Cochliobolus sativus (Conidia form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as Uromyces appendiculatus;
Puccinia species, such as Puccinia recondita;
Sclerotinia species, such as Sclerotinia sclerotiorum; Tilletia species, such as Tilletia caries;
Ustilago species, such as Ustilago nuda or Ustilago avenae;
Pellicularia species, such as Pellicularia sasakii;
Pyricularia species, such as Pyricularia oryzae;
Fusarium species, such as Fusarium culmorum;
Botrytis species, such as Botrytis cinerea;
Septoria species, such as Septoria nodorum;
Leptosphaeria species, such as Leptosphaeria nodorum;
Cercospora species, such as Cercospora canescens;
Alternaria species, such as, for example, Altemaria brassicae;
Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.
The good plant tolerance of the active substances in the concentrations required for controlling plant diseases permits the treatment of above-ground plant parts, of plant material and seed and of the soil.
The active substances according to the invention can be particularly successfully used for controlling diseases in viticulture, fruit cultivation and vegetable cultivation, such as against Venturia, Podosphaera, and Plasmopara species. Rice diseases, such as Pyricularia species, are also successfully controlled.
In material protection, the substances according to the invention can be used for the protection of technical materials from attack and destruction by undesired microorganisms.
In the present context, technical materials are to be understood as meaning nonliving materials which have been prepared for use in industry. For example, technical materials which are to be protected by active substances according to the invention against microbial change or destruction may be adhesives, glues, paper and cardboard, textiles, leather, wood, coating materials and plastics articles, cooling lubricants and other materials which may be attacked or decomposed by microorganisms. Parts of production plants, for example cooling circulations, which may be impaired by multiplication of organisms may also be mentioned among the materials to be protected. In the present invention, preferably adhesives, glues, papers and cardboards, leather, wood, coating materials, cooling lubricants and heat-transfer liquids may be mentioned as technical materials, particularly preferably wood.
For example, microorganisms of the following genera may be mentioned:
Altemaria, such as Altemaria tenuis,
Aspergillus, such as Aspergillus niger,
Chactomium, such as Chaetomium globosum,
Coniophora, such as Coniophora puetana,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium versicolor,
Aureobasidium, such as Aureobasidiuin pullulans,
Sclerophomiia, such as Sclerophoma pityophila,
Trichoderma, such as Trichoderma viride,
Esclierichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.
The active substances according to the invention which have good plant tolerance and advantageous toxicity with respect to warm-blooded animals are also suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in horticulture, in the protection of stored goods and materials and in the hygiene sector or in the area of veterinary medicine. The substances are effective against normally sensitive and resistant species and against pests in all or individual stages of development. The abovementioned animal pests include:
From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
From the order of the Diplopoda, for example Blaniulus guttulatus.
From the order of the Chilopoda, for example Geophilus carpophagus, Scutigera spec.
From the order of the Symphyla, for example Scutigerella immaculata.
From the order of the Thysanura, for example Lepisma saccharina.
From the order of the Collembola, for example Onychiurus armatus.
From the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leticophaea maderae, BlattelIa germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
From the order of the Dermaptcra, for example Forficula auricularia.
From the order of the Isoptera, for example Reticulitermes spp.
From the order of the Anoplura, for example Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
From the order of the Mallophaga, for example Trichodectes spp., Damalinea spp.
From the order of the Thysanoptera, for example Hercinothrips femoralis, Thrips tabaci.
From the order of the Heteroptera, for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiplium avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
From the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella,
Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuchniella, Galleria mclonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podania, Capua rcticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.
From the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodenna spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon soistitialis, Costelytra zealandica.
From the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomonrum pharaonis, Vespa spp.
From the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Osciniella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
From the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp.
From the order of the Arachnida, for example Scorpio maurus, Latrodectus mactans.
From the order of the Acarina, for example Acarus siro, Argas spp., Omithodoros spp., Dennanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Aniblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonyclius spp., Tetranyclius spp.
The phytoparasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.
The substances which can be used according to the invention can be particularly successfully employed for controlling plant-damaging mites, such as against the bean spider mite (Tetranychus urticae), or for controlling plant-damaging insects, such as against the caterpillars of the diamond-back moth (Plutella maculipennis), the larvae of the horseradish leaf beetle (Phaedon cochleariae), and the green rice cicada (Nephotettix cincticeps).
The substances which may be used according to the invention act not only against plant pests, hygiene pests and pests of stored goods but also in the veterinary medical sector against animal parasites (ectoparasites), such as scale ioxodid ticks, argasidae, mange mites, trombiidae, flies (biting and licking), parasitic fly larvae, lice, biting lice, bird lice and fleas. These parasites include:
From the order of the Anoplurida, for example Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
From the order of the Mallophagida and the suborders Amblycerina and Ischnocerina, for example Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Wenieckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
From the order of Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anoplieles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Clirysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haeniatopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophiaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.
From the order of the Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
From the order of the Heteroptenrda, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
From the order of the Blattarida, for example Blatta orientalis, Periplaneta americana, Blattela gernanica, Supella spp.
From the subclass of the Acaria (Acarida) and the orders of the Meta- and Mesostigmata, for example Argas spp., Omithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Derrnacentor spp., Haemophysalis spp., Hyalomma spp., Rlhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Stemostoma spp., Varroa spp.
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornitliocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.
The active substances according to the invention are also suitable for increasing the harvest yield. In addition, they have low toxicity and possess good plant tolerance.
Depending on their respective physical and/or chemical properties, the active substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very finely encapsulated forms in polymeric substances and in coating materials for seed and ULV cold and warm mist formulations.
These formnulations are prepared in a known manner, for example by mixing the active substances with extenders, that is to say liquid solvents, liquefied gases under pressure and/or solid carriers, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or form-producing compositions. In the case of the use of water as an extender, for example, organic solvents may also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaplithalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. mineral oil fractions, alcohols such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water. Liquefied gaseous extenders or carriers are those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenohydrocarbons and butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for examnple, crushed natural minerals, such as kaolins, aluminas, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and crushed synthetic minerals, such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: for examnple, crushed and fractionated natural minerals, such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic powders and granules of organic material, such as sawdust, coconut shells, maize cobs and tobacco stems. Suitable emulsifiers and/or form-producing compositions are: for example, nonionic and anionic emulsifiers, such as polyoxyethiylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulplionates and protein hydrolysis products. Suitable dispersants are: for example, ligninsulplite waste liquors and methylcellulose.
Adherents, such as carboxyrnethylcellulose, natural and synthetic pulverulent, granular or latex-like polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipids, such as kephalins and lecithins, and synthetic phospholipids. Further additives may be mineral and vegetable oils.
Colorants, such as inorganic pigments, e.g. iron oxide, titanium oxide, Prussian blue, and organic dyes, such as alizarin, azo and metal phthalocyanine dyes, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc, may be used.
The formulations contain in general between 0.1and 95 per cent by weight of active substance, preferably between 0.5 and 90%.
Depending on their respective physical and/or chemical properties, the active substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very finely encapsulated forms in polymeric substances and in coating materials for seed, and ULV cold mist and warm mist formulations.
The active substances according to the invention can be used, as such or in their formulations, also as a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the action spectrum or to prevent the development of resistance. In many cases, synergistic effects are obtained, i.e. the activity of the mixture is greater than the activity of the individual components.
Suitable components of the mixture are, for example, the following compounds:
Fungicides:
aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
benalaxyl, benodanil, benomyl, benzamacril, benzamacryl-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
calcium polysulphide, capsimycin, captafol, captan, carbendazim, carboxin, carvon, chinomethionate (quinomethionate), chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuiram,
debacarb, dichlorophen, diclobutrazol, diclofluanid, diclomezine, diclorane, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon,
ediphenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,
famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide, fluquinconazole, flurprimidol, flusilazol, flusulfamide, flutolanil, flutriafol, folpet, fosetyl aluminium, fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazol-cis, furmecyclox,
guazatine,
hexachlorobenzene, hexaconazole, hyinexazol,
imazalil, iImnibenconiazole, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (UBP), iprodione, irumamycin, isoprothiolane, isovaledione,
kasugamycin, kresoxime-methIyl, Copper formulations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture,
mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil, metalaxyl, metconazol, methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,
nickel dimethyidithiocarbamate, nitrothal-isopropyl, nuarimol,
ofurace, oxadixyl, oxamocarb, oxolinicacide, oxycarboxim, oxyfenthiine,
paclobutrazol, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidon, propamnocarb, propanosine sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,
quinconazole, quintozene (PCNB),
Sulphur and sulphur formulatons,
tebuconazole, tecloflalamn, tecnazene, tetcyclacis, tetraconazole, thiabendazol, thicyofen, thilfluzanide, tlliophaniate-methyl, thirain, tioxymid, tolclofos-methyl, tolylfluanlid, triadiniefon, triadimenol, triazbutil, triazoxide, trichiamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazol,
uniconazole,
validamycin A, vinclozolin, viniconazole,
zarilamid, zineb, ziram and
Dagger G,
OK-8705,
OK-8801,
xcex1-(1,1-dimethylethyl)-xcex2-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,
xcex1-(2,4-dichlorophenyl)-xcex2-fluoro-b-propyl-1H-1,2,4-triazole-1-ethanol,
xcex1-(2,4-dichlorophenyl)-xcex2-methoxy-a-methyl-1H-1,2,4-triazole-1-ethanol,
xcex1-(5-methyl-1,3-dioxan-5-yl)-xcex2-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol, (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,
(E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,
1-isopropyl {2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate
1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenylmethyl)-oxime,
1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,
1-(3,5-diclorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,
1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,
1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,
1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,
1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,
1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol,
2xe2x80x2,6xe2x80x2-dibromo-2-mnethyl-4xe2x80x2-trifluoromethoxy-4xe2x80x2-trifluoro-methyl-1,3-tiliazole-5-carboxanilide,
2,2-dichloro-N-[1-(4-chlorophenyl)-etliyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,
2,6-dichloro-5-(methylthio)-4-pyrimidinyl thiocyanate,
2,6-dichloro-N-(4-trifluoromnethylbenzyl)-benzamide,
2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,
2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,
2-[(1-methyletihyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,
2-[[6-deoxy-4-O-(4-O-methyl-xcex2-D-glycopyranosyl)-a-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,
2-aminobutane,
2-bromo-2-(bromomethyl)-pentanedinitrile,
2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,
2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,
2-phenylphenol(OPP),
3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,
3,5-dichloro-N-[cyan[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,
3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,
4-chloro-2-cyan-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,
4-methyl-tetrazolo[1,5-a]-quinazolin-5(4H)-one,
8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,
8-hydroxyquinoline sulphate,
9H-xanthene-9-carboxylic acid 2-[(phenylamino)-carbonyl]-hydrazide,
bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2, 5-thiophene dicarboxylate,
cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,
cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholine hydrochloride,
ethyl[(4-chlorophenyl)-azo]-cyanoacetate,
potassium bicarbonate,
methlaietetrathiol sodium salt,
methyl 1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,
methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,
methyl N-(cliloroacetyl)-N-(2,6-dimetihylphenyl)-DL-alaninate,
N-(2,3-dichloro-4-hydroxypherlyl)-1-metliyl-cyclohexancarboxaniide.
N-(2,6-dirnethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,
N-(2,6-dimetliylplcyi)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,
N-(2-clhloro-4-tiitroplenyl)-4-mcthyl-3-nitro-benzolsulpllonamide,
N-(4-cycloliexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,
N-(4-hexylplhenyl)-1,4,5,6-tetralydro-2-pyrimidinaniine,
N-(5-chloro-2-methylphenyl)-2-netiloxy-N-(2-oxo-3-oxazolidinyl)-acetamide,
N-(6-metlhoxy)-3-pyridinyl)-cyclopropanecarboxamide,
N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,
N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-Nxe2x80x2-methoxy-methaneimidoamide,
N-formyl-N-hydroxy-DL-alanine sodium salt,
O,O-diethyl-[2-(dipropylamino)-2-oxocthyl]-ethylphosphoramidothioate,
O-methyl S-phenyl phenylpropylphosphoramidothioate,
S-methyl 1,2,3-benzothiadiazole-7-carbothioate,
spiro[2H]-1-benzopyran-2,1xe2x80x2(3xe2x80x2H)-isobenzofuran]-3xe2x80x2-one,
Bactericides:
bronopol, dichlorophen, nitrapyrin, nickel dimethyidithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate und other copper formulations.
Insecticides/Acaracides/Nematicides:
abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin,
bacillus thuringiensis, 4-Bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim, butylpyridaben,
cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan, cartap, chloethocarb, chlorethioxyfos, clilorfenapyr, chlorfenvinpihos, chliorfluazuron, chlonnephos, N-[(6-cilloro-3-pyriditlyl)-niethyl]-Nxe2x80x2-cyano-N-methyl-ethaneimidoamide, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyflutlirin, cylialotlirin, cyhexatin, cypermethrin, cyromazine,
deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulphoton,
edifenphos, emamectin, esfen valerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimphos,
fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, ftirathiocarb,
HCH, heptenophos, hexaflumuron, hexythiazox,
imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivermectin, lamnda-cyhalothrin, lufenuron,
malathion, mecarbam, mevinphos, mesulphenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,
naled, NC 184, nitenpyram
omethoate, oxamyl, oxydemethon M, oxydeprofos,
parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, plioxim, pirimicarb, pirimiphos M, pirimiphos A, profenophos, promecarb, propaphos, propoxur, prothiophos, prothoate, pymetrozine, pyrachlophos, pyridaphenthion, pyresnietlirin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen,
quinalphos,
salithion, sebufos, silafluofen, sulphotep, suiprofos,
tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin, triarathene, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb,
vamidothion, XMC, xylylcarb, zetamethrin.
A mixture with other known active substances, such as herbicides, or with fertilizers and growth regulators, is also possible.
The active substances can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusting agents and granules. They are used in a customary manner, for example by pouring, spraying, atomizing, broadcasting, dusting, foam application, brushing, etc. It is also possible to apply the active substances by the Ultra-Low-Volume method or to inject the active substance formulation or the active substance itself into the soil. The seed of the plants may also be treated.
When the active substances according to the invention are used as fungicides, the application rate may be varied within a relatively large range, depending on the method of application. In the treatment of plant parts, the application rates of active substance are in general between 0.1 and 10,000 g/ha, preferably between 10 and 1000 g/ha. In the treatment of seed, the application rates of active substance are in general between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the application rates of active substance are in general between 0.1 and 10,000 g/ha, preferably between 1 and 5000 g/ha.
The compositions used for protecting technical materials contain the active substances in general in an amount of 1 to 95%, preferably of 10 to 75%.
The use concentrations of the active substances according to the invention depend on the type and occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal amount for use can be determined by test series. In general, the use concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.
The activity and the action spectrum of the active substances to be used according to the invention in material protection or of the compositions, concentrates or very generally formulations which can be prepared therefrom can be increased if optionally further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active substances are added for increasing the action spectrum or achieving special effects, such as, for example, additional protection from insects. These mixtures may have a broader action spectrum than the compounds according to the invention.
Even when used against animal pests, the substances according to the invention may be present as a mixture with synergistic agents in commercial formulations and in the use forms prepared from these formulations. Synergistic agents are compounds by means of which the action of the active substances is increased without the added synergistic agent itself having to be actively effective.
The active substance content of the use forms prepared from the commercial formulations may vary within wide ranges. The active substance concentration of the use forms may be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
Application is effected in a customary manner adapted to one of the use forms.

Nitrophenyl-sulphonyl-imidazoles and use thereof for controlling vegetable and animal pests

Abstract: wherein X, R1, R2 and R3 have the meanings stated in the description, a process for the preparation of the novel substances and their use for controlling vegetable and animal pests.


A user may interact with an interactive remote display (e.g., touch input) and the interaction may be sent to an application on a mobile device. The mobile device (application and/or encoder) may render frames for the display when there is a change. Latency in the pipeline may be alleviated by determine a rendering rate for an application. A dummy frame may be sent to the encoder if the application is not a constant rendering type of application. The dummy frames may be sent subsequent to the rendered frames to flush the pipeline.

In a streaming video system, video frames may be rendered by an encoder. The encoder, for example, may compress the video stream and/or encode the video stream in a format and/or resolution that is compatible with the display on which it is to be shown. The connection between the device rendering the video and the display may be a wired (e.g., USB) or wireless (e.g., WiFi, Bluetooth) connection. A decoder associated with the display may decode the encoded video frames it receives. When video is rendered at a constant frame rate, the display may be continuously updated with new frames.


The invention herein includes enhancing the surface of an amorphous silicon hardmask through implantation of nonpolar, hydrophobic elements, resulting in increased hydrophobicity and increased resist adhesion of the amorphous silicon surface. According to the invention, implanting the hydrophobic elements may involve introduction of the hydrophobic elements into the surface of the amorphous silicon by way of low energy implantation and plasma treatment. The implanted hydrophobic element may be Boron, Xenon, Fluorine, Phosphorus, a combination thereof, or other hydrophobic elements. According to the invention, the surface of the amorphous silicon is enhanced with 10-15% hydrophobic element, however in other embodiments, this composition may be adjusted as needed. In any case, however, the invention herein includes maintaining an etch selectivity of the bulk amorphous silicon hardmask.

The present invention relates generally to semiconductor device fabrication, and more particularly to patterning directly on an amorphous silicon hardmask.
In semiconductor device manufacturing, patterning directly on an amorphous silicon (a-Si) hardmask is difficult to achieve with high resolution due to poor adhesion between the a-Si hardmask and a subsequent resist layer. In typical practice, this adhesion at high resolutions requires deposition of an intermediary layer to facilitate adhesion, known as an organic layer. However, incorporating additional planar layers such as the organic layer not only results in additional resource expenditures, such as cost and time, but also increases integrated circuit complexity as the organic layer need be later removed.

Patterning directly on an amorphous silicon hardmask

International Business Machines Corporation


Systems and methods for determining the position of a buoyancy element in a marine survey are described in which a passive reflecting material is disposed on the buoyancy element to enable a radar on the vessel to detect the position of the buoyancy element. The radar may emit a frequency modulated continuous wave or a sequence of frequency modulated or phase modulated sinusoidal waves.

This disclosure relates to marine seismic data acquisition, and more particularly to technology for positioning a front portion of an array of streamers.
Seismic exploration involves surveying subterranean geological formations for hydrocarbon deposits. A seismic survey typically involves deploying seismic source(s) and seismic sensors at predetermined locations. The sources generate seismic waves, which propagate into the geological formations creating pressure changes and vibrations along their way. Changes in elastic properties of the geological formation scatter the seismic waves, changing their direction of propagation and other properties. Part of the energy emitted by the sources reaches the seismic sensors. Some seismic sensors are sensitive to pressure Changes (hydrophones), others to particle motion (e.g., geophones), and industrial surveys may deploy only one type of sensors or both. In response to the detected seismic events, the sensors generate electrical signals to produce seismic data. Analysis of the seismic data can then indicate the presence or absence of probable locations of hydrocarbon deposits.
Some surveys are known as "marine" surveys because they are conducted in marine environments. However, "marine" surveys may be conducted not only in saltwater environments, but also in fresh and brackish waters. In one type of marine survey, called a "towed-array" survey, an array of seismic sensors and source(s) is towed behind a survey vessel. The seismic sensors are contained within or on streamers towed by the survey vessel.
In cases where multiple streamers are used for seismic data acquisition, deflector devices (e.g., doors and/or mono-wings, etc.) are often used to maintain streamer separation. Lead-in devices are then used to connect the vessel to the deflectors. In order to maintain the streamer depth at the front of the array, floats or paravanes are used to get sufficient buoyancy of the front, and hence avoid the front to dive. In order to determine the position of the streamers, GPS units have often been used on the floats or on special dedicated front end positioning floats. These floats are cumbersome and difficult to maintain as they are sitting on the front of the streamers. Furthermore, they require increased mobilization time and hence make the operation less efficient.
Another drawback of having the GPS on the float is that it needs power and such power comes from the lead-in or the streamer as battery power is not sufficient for powering the GPS and its associated communication radio. Since the deflectors are large, and ropes and chains used to connect the paravane and wings are exposed to large forces, it is difficult to maintain electrical wiring from the streamers to the floats. In addition, extra equipment is needed to connect a front end GPS.
U.S. Pat. No. 7,315,274 to Kongsberg Seatex AS discloses a method for determining the position of marine vessels and objects through the use of an interrogator and transponder. The '274 patent describes the use of the transponder for including identity tags into the signal to be reflected to the interrogator. Such method, however, still requires power on the marine objects on which the transponders are positioned.

Method for positioning the front end of a seismic spread


A shellfish cracking device for cracking shellfish such as lobster and crabs is provided. The shellfish cracking device includes a first cracking member having a first handle portion, middle portion, and blade portion; and a second cracking member having a second handle portion, middle portion, and blade portion. The first blade portion has a substantially concaved surface, and the second blade portion has a substantially rounded surface which engage each other to crack the shell. The second blade portion has a substantially linear, tapered cutting edge for cracking the shell forcefully and cleanly.

The present invention generally relates to a device for cracking shellfish. Particularly, this invention relates to a scissors-like device for cutting shellfish such as lobster and crabs sharply and cleanly.
Many people in ocean communities and elsewhere enjoy eating shellfish such as lobsters and crabs. Shellfish can be enjoyed in a wide variety of settings. People like to order shellfish in restaurants, prepare shellfish meals in the home, or attend outdoor lobster/crab bakes. Eating the meat of shellfish often involves a difficult first step of cracking and opening the shells. Then, the meat must be picked out of the cracked shells carefully to avoid ingesting splintered shell pieces. People use various utensils such as knives, nutcrackers, forks, and small hammers in this rather complex operation, but such utensils frequently are ineffective. It is often hard to grasp the claws, lobster tails, and other shell pieces with these common utensils. The wet shell sections tend to slip and slide off the utensils. Once the shells finally are gripped so that they may be cracked, the shells may not break easily or cleanly. The pieces of the shell, water and seafood will splatter everywhere during the cracking step. Some shellfish fans enjoy this part of the shellfish eating experience and view extracting seafood from the shell as an exciting challenge. Other people enjoy eating shellfish but would like to do so in a more refined and less exasperating manner.
Various shellfish cracking tools are known in the art to assist in the cracking of shells and eating of shellfish meat. For example, Saizon, U.S. Pat. No. 6,019,673 discloses a utensil for cracking the shells of crabs, lobsters, and other shellfish. The Saizon utensil includes a pair of handles that are pivotally connected. Each handle has a jaw with a tapered cutting edge for cracking the shells. The handles are bent in such a way as to prevent complete closure of the jaws, so that the shell is cracked while leaving the meat of the shellfish intact.
Scott, Jr., U.S. Pat. No. 4,716,627 discloses a plier-like tool for cracking and opening crab claws. The tool has jaws with concaved portions for gripping and cracking the crab claws. The end of the tool has a curved needle nose portion with teeth thereon for picking out the exposed meat.
Walker, U.S. Pat. No. 4,519,136 discloses a shellfish cutting and eating implement having first and second lever members pivotally connected together. The first lever member includes a jaw portion and a flared end to keep the jaw in the proper position during the cutting operation. The flared end also defines a pointed forward end, in the shape of a fork, to facilitate spearing and removal of the shellfish meat. The second lever member includes a jaw portion which defines a notched cutting edge.
Latorella, U.S. Pat. No. 4,103,395 discloses a shellfish tool comprising first and second lever units pivotally connected to each other. Each lever unit comprises an elongated handle portion, a shoulder portion, and an elongated jaw portion. The handle portions are provided with cracker sections which can be used to crack the shells. The tool also includes a spring means which biases the first and second lever units so that the jaw portions are engaged with each other and the handle portions are removed from each other. In another step, The handle portions move toward one another against the pressure of the spring to cause the jaw portions to separate.
Although some conventional shellfish cracking tools can be effective in cracking some shells, there is still a need for an improved cracking device that cracks and cuts-through hard shells cleanly and efficiently. The desired shellfish cracking device should be capable of holding the shell tightly so that it does not slip during the cracking step. The present invention provides such a shellfish cracking device. These and other objects, features, and advantages of this invention are evident from the following description and attached figures.


A decoder for a memory device includes driving devices each applying a respective line voltage to a respective line of the memory device when turned on. The decoder also includes a control device coupled to the plurality of driving devices at a common node for generating a voltage that controls the driving devices to turn on or off. Also, a capacitor coupled to the common node increases the voltage at the common node from an initial boost voltage to a final boost voltage. Thus, a line of a memory device is driven to a boost voltage with minimized area and wiring complexity.

FIG. 1 shows a typical flash memory device 100 including blocks of flash memory cells. The elements of one example block 102 include an array of flash memory cells 103. An array of eight by eight flash memory cells is illustrated in the example block 102 for simplicity of illustration and description. However, a typical block would have more numerous flash memory cells.
Each flash memory cell 103 has a control gate, a drain, and a source. The control gates of all flash memory cells in one row are coupled to a same word-line. The drains of all flash memory cells in one column are coupled to a same bit-line. Thus, the example block 102 has the eight word lines WL0, WL1, . . . , and WL7 for the eight rows of flash memory cells. In addition, the example block 102 has eight bit lines coupled to eight select MOSFETs (metal oxide semiconductor field effect transistors) 104.
Furthermore, the example block 102 has a local X-decoder 106 for activating one of the word lines WL0, WL1, . . . , and WL7. For accessing one of the flash memory cells in the block 102, a selected one of the word lines WL0, WL1, . . . , and WL7 is activated when a boost voltage VBST is applied thereon by the local X-decoder. Additionally for accessing that flash memory cell, one of the select MOSFETs 104 coupled to the drain of that flash memory cell is turned on for applying a boost voltage YBST thereon. The sources of the flash memory cells are coupled to a low supply voltage VSS.
Further referring to FIG. 1, the local X-decoder 106 applies the boost voltage VBST on the selected one of the word lines WL0, WL1, . . . , and WL7 using the controls signals PGW and NGW from a global X-decoder 108, WLG from a vertical block decoder 110, and eight word-line voltages AVW0, AVW1, . . . , and AVW7 from a vertical word line decoder 112. The PGW signal indicates whether a flash memory cell within the block 102 is to be accessed for an operation such programming, and NGW is the reverse logical state of PGW. The global X-decoder decodes block row address bits from an address sequencer (not shown) for generating PGW and NGW that are applied across a row of blocks such as 102 and 114 in FIG. 1.
The WLG indicates whether a column of blocks such as blocks 102 and 116 are being accessed. The vertical block decoder 110 decodes vertical block address bits from the address sequencer (not shown) for generating WLG applied across the column of blocks 102 and 116 in FIG. 1.
The vertical word line decoder 112 decodes vertical word line address bits from the address sequencer (not shown) for generating eight word-line voltages AVW0, AVW1, . . . , and AVW7 applied across the column of blocks 102 and 116. In addition, the drain bit line boost voltage YBST is applied on the selected drain bit line across the column of blocks 102 and 116. FIG. 1 shows an array of two by two blocks for the flash memory device 100, but typical flash memory devices typically include more numerous blocks.
FIG. 2 shows an example implementation 106A of the local X-decoder 106 as disclosed in U.S. Pat. No. 6,646,950. The local X-decoder 106A inputs the control signals PGW, NGW, WLG, AVW0, AVW1, . . . , and AVW7 from the decoders 108, 110, and 112. The local X-decoder 106A then applies a boost voltage VBST on one of the word lines WL0, WL1, . . . , and WL7 when the PGW is a logical high state.
Referring to FIG. 2, the local X-decoder 106A includes a respective driver for each of the word lines WL0, WL1, . . . , and WL7. Thus, a first driver 120 is for the first word line WL0, a second driver 121 is for the second word line WL1, . . . , and so on until an eighth driver 127 is for the eighth word line WL7.
Each driver, such as the first driver 120, includes a driving MOSFET (metal oxide semiconductor field effect transistor) 132 and a pull-down MOSFET 134 coupled in series. The driving MOSFET 132 has a drain coupled to a corresponding line voltage AVW0 from the vertical word line decoder 112. Thus, the driving MOSFET within the second driver 121 is coupled to the corresponding line voltage AVW1, and so on until the driving MOSFET within the eighth driver 127 is coupled to the corresponding line voltage AVW7.
Further in the example driver 120, the source of the driving MOSFET 132 is coupled to a drain of the pull-down MOSFET 134. The source of the pull-down MOSFET 134 is coupled to a low voltage VSS. The control signal NGW from the global X-decoder 108 is coupled to the gate of the pull-down MOSFET 134. The example driver 120 also includes a control MOSFET 136 having a source coupled to the gate of the driving MOSFET 132 at a control node 138.
Further referring to FIG. 2, each of the drivers 120, 121, . . . , and 127 are each implemented similarly with a respective control MOSFET, a respective driving MOSFET, and a respective pull-down MOSFET. The PGW control signal from the global X-decoder 108 is applied on the drains of the control MOSFETs in all of the drivers 120, 121, . . . , and 127. The WLG control signal from the vertical block decoder 110 is applied on the gates of the control MOSFETs in all of the drivers 120, 121, . . . , and 127.
For driving one of the word lines WL0, WL1, . . . , and WL7 to a boost voltage VBST, the controls signals PGW and WLG are set at the boost voltage VBST. Assume that the first word line WL0 is to be activated to the boost voltage VBST. In that case, initially, the AVW0 is set to the low voltage VSS while the control signals PGW and WLG are set to the original boost voltage VBST. With such voltages, an initial boost voltage (VBST−Vth) is generated at the control node 138, with Vth being the threshold voltage of the control MOSFET 136.
Thereafter, with the control signals PGW and WLG still set to the original boost voltage VBST, the AVW0 is set to the original boost voltage VBST such that a final boost voltage (VBST+ΔV) is generated at the control node 138, with ΔV being about the gate to source voltage of the driving MOSFET 132. In this manner, the original boost voltage VBST is generated on the word line WL0 without degradation of the voltage level from the gate to source voltage drop for the driving MOSFET 132 when the AVW0 is set to the original boost voltage. On the other hand, if the AVW0 is the low voltage VSS, then the word line WL0 is discharged to the low voltage VSS.
The respective control MOSFET, the respective driving MOSFET, and the respective pull-down MOSFET within each of the other drivers 121, . . . , and 127 operate similarly. Thus, the corresponding word line WL is activated to the boost voltage VBST if the corresponding line voltage AVW is the boost voltage, or is discharged to the low voltage VSS if the corresponding line voltage AVW is the low voltage VSS, for each of the drivers 120, 121, . . . , and 127.
When the NGW is activated to the boost voltage VBST (with the PGW being deactivated to the low voltage VSS), the driving MOSFETs are turned off, and the pull-down MOSFETs are turned on in all of the drivers 120, 121, . . . , and 127. In that case, each of the word lines WL0, WL1, . . . , and WL7 is discharged to the low voltage VSS.
In the local X-decoder 106A of FIG. 2, each of the drivers 120, 121, . . . , and 127 is implemented with a corresponding control MOSFET 136 for stepping up the control voltage at a respective control node 138 from the initial boost voltage (VBST−Vth) to the final boost voltage (VBST+ΔV) that is higher than the original boost voltage VBST. Thus, eight such control MOSFETs and eight separate such control nodes are used in the eight drivers 120, 121, . . . , and 127 in the prior art of FIG. 2, resulting in increased area and wiring complexity.