In a sewage treatment plant with a membrane bioreactor (MBR), raw untreated or partially treated wastewater (influent) and/or mixed liquor in the intensified process is superoxygenated. In a preferred form of the process the influent is superoxygenated such that membrane air scouring requirements are reduced. Influent may be fed to a swing zone where denitrification and nitrification occur simultaneously through process control. In one embodiment superoxygenation is conducted in an internal recycle stream of the mixed liquor, with oxygen content supersaturated preferably to over 300 parts per million. Due to the active evolution of oxygen gas from the supersaturated stream, occurring preferably by seeding the supersaturated stream with air bubbles, the supersaturated oxygen can serve the dual purposes of meeting process oxygen demands and providing part of air scouring requirements for the membranes.

This invention concerns sewage treatment processes and systems, and particularly involves a method and system used in a plant having membrane bioreactors for intensifying a treatment process, sometimes lowering air scour requirements through superoxygenation of raw wastewater feed (influent) or mixed liquor in the MBR tank, while providing needed oxygen for the intensified process. The method of oxygenating the influent can also break down refractory organics, improving process efficiency.
Membrane air scouring is necessary to remove the solids that accumulate during filtration and generally accounts for 25%-75% of total overall system energy demand. Due to inefficient diffusers and oxygen transfer rate (OTR) limitations, much of the oxygen contained in scouring air is wasted to the atmosphere instead of being used for biological processes. Moreover, increasing mixed liquor suspended solids (MLSS) concentration for the purposes of reducing process volumes further reduces OTR, requiring systems to be larger and more complicated to operate. This invention uses a stream of supersaturated influent and/or mixed liquor to provide all or most of the biological process oxygen, while also in most cases reducing the amount of air required for membrane scouring purposes. This invention reduces the need for diffused aeration. The term "supersaturate" with oxygen as used herein means to introduce more oxygen into solution than normally can be retained in the liquid if in an open tank at ambient conditions, i.e. atmospheric pressure (which is about 10 mg/l).
Most submerged MBR technologies use diffused aeration to scour away materials that accumulate on membrane surfaces during filtration (so-called jet aeration is an alternative). Generally, coarse bubble aeration has been shown to be the most efficient means of air scouring but it is the least efficient means of delivering oxygen to the biological process. Given increasing energy costs, some manufacturers have turned to fine-bubble diffusers for better oxygen delivery and to provide air scouring, with attendant maintenance issues and increased equipment costs. Regardless of the aeration technology used to provide scouring air, the oxygen transfer rate (OTR) limits how much a biological process can be intensified (volume reduced) as diffuser performance drops off precipitously with increasing mixed liquor suspended solids concentrations (MLSS).
Prior oxygenation systems have been proposed that introduce (pure) oxygen into mixed liquor through agitation or mixing. However, these technologies introduce oxygen into other zones in the biological flow sheet and not directly into the influent or the MBR tank, and none has suggested utilizing the supersaturated oxygen to meet some of the membrane air scour requirements.
Due to increased energy costs, it would be greatly advantageous if supersaturation of oxygen could be used in an MBR system for process enhancement through increased oxygen content and also, in most cases, for scouring aeration to thereby reduce separate air scour requirements.

Membrane bioreactor with reduced air scour requirements


An integrated circuit fabrication process is provided for forming relatively thin sidewall spacers extending laterally from upper portions of opposed sidewall surfaces of a transistor gate conductor which resides partially within a trench of a semiconductor substrate. The present invention contemplates etching a trench through a masking layer and partially through a silicon-based substrate arranged underneath the masking layer. A gate dielectric is then formed upon silicon-based surfaces which border the trench. A conformal dielectric layer is deposited across the masking layer and the gate dielectric, followed by the deposition of a gate conductor material across the dielectric layer. The gate conductor material and the dielectric layer are removed from above the upper surface of the masking layer. Portions of the dielectric layer interposed between the masking layer and the gate conductor are etched to a level commensurate with the substrate surface. An LDD implant self-aligned to the lateral boundaries of the masking layer and the gate conductor sidewall surfaces is forwarded into the substrate underneath the trench. Relatively thin oxide spacer structures are then thermally grown upon the sidewall surfaces of the gate conductor. After removing the masking layer, a source/drain implant is performed. In another embodiment, the gate conductor is formed between the opposed lateral boundaries of the masking layer upon the gate dielectric. A source/drain implant is performed after removing the masking. Relatively thin dielectric spacers are formed upon the upper portions of the sidewall surfaces of the gate conductor by depositing and anisotropically etching a dielectric.

1. Field of the Invention
This invention relates to integrated circuit fabrication and, more particularly, to relatively thin sidewall spacers extending laterally from upper portions of opposed sidewall surfaces of a transistor gate conductor which resides partially within a trench of a semiconductor substrate.
2. Description of the Related Art
Fabrication of a MOSFET device is well known. Generally speaking, MOSFETs are manufactured by placing an undoped polycrystalline ("polysilicon") material over a relatively thin gate oxide. The polysilicon material is then patterned to form a gate conductor directly above a channel region of the substrate. A dopant species is implanted into the gate conductor and regions of the substrate exclusive of the channel region, thereby forming source and drain regions adjacent to and on opposite sides of the channel region. If the dopant species used for forming the source and drain regions is n-type, then the resulting MOSFET is an NMOSFET ("n-channel") transistor device. Conversely, if the dopant species is p-type, then the resulting MOSFET is a PMOSFET ("p-channel") transistor device. Integrated circuits utilize either n-channel devices exclusively, p-channel devices exclusively, or a combination of both on a single substrate. While both types of devices can be formed, the devices are distinguishable based on the dopant species used.
While in operation, transistors which have heavily doped source and drain regions arranged laterally adjacent the gate conductor often experience a problem known as hot carrier injection ("HCI"). HCI is a phenomena in which the kinetic energy of charged carriers (holes or electrons) within the channel region is increased as the carriers are accelerated through large potential gradients. As a result of this increase in kinetic energy, the charged carriers are injected into the gate oxide wherein they may become trapped. The greatest potential gradient, often referred to as the maximum electric field ("Em") occurs near the drain during saturated operation. As a result of carrier entrapment within the gate oxide, a net negative charge density forms in the gate oxide. The trapped charge can accumulate with time, resulting in a positive threshold shift in a NMOS transistor, or a negative threshold shift in a PMOS transistor.
To overcome problems of sub-threshold current and threshold shift resulting from HCI, an alternative drain structure known as the lightly doped drain ("LDD") is commonly used. The purpose of the LDD is to absorb some of the potential into the drain and thus reduce Em. A conventional LDD structure is one in which a light concentration of dopant is self-aligned to the gate conductor followed by a heavier concentration of dopant self-aligned to the gate conductor on which a pair of sidewall spacers has been formed. The purpose of the first implant dose is to produce lightly doped sections within an active area of the substrate near the channel. The second implant dose is spaced from the channel by a distance substantially equivalent to the thickness of each sidewall spacer. The second implant dose forms heavily doped source and drain regions within the active area laterally outside the LDD areas. In this manner, the lateral thickness of each sidewall spacer dictates the length of each LDD area.
Unfortunately, the addition of LDD areas adjacent the channel adds parasitic resistance to the source-drain pathway, leading to many deleterious effects. For example, the parasitic resistance causes an increase in the value of the gate-to-source voltage, V.sub.GS, required for the drive current, I.sub.D, (i.e., current flowing between the source and drain regions of a transistor in its on-state) to reach saturation. Therefore, in order to reduce the parasitic resistance of the source-drain pathway, it has become necessary to reduce the lateral dimensions of the LDD areas. However, the length of each LDD area cannot be reduced below a specific dimension using conventional methods. In particular, the lateral thickness of the sidewall spacers used to define LDD areas generally has a limited minimum size. The sidewall spacers are typically formed by chemically-vapor depositing a layer of spacer material across the substrate and the gate conductor arranged above the substrate. The spacer material is thusly placed upon the opposed sidewall surfaces of the gate conductor, the upper surface of the gate conductor, and the upper surface of the substrate exterior to the gate conductor. The spacer material is then anisotropically etched such that it is removed from horizontally oriented surfaces faster than from vertically oriented surfaces. The duration of the anisotropic etch is preferably terminated after the spacer material has been removed from a significant portion of the horizontally oriented surfaces but before the spacer material can be completely removed from the vertically extending sidewall surfaces.
Although chemical-vapor deposition ("CVD") is not as vertically-directed as physical vapor deposition, a CVD deposited material still tends to accumulate more quickly upon horizontally oriented surfaces than upon vertically oriented surfaces. The accumulation of the CVD deposited material is particularly poor upon tall vertical surfaces. The thickness of a gate conductor, and hence the height of the sidewall surfaces which bound the gate conductor, must be maintained above, e.g., 200 .ANG., to ensure that the conductivity of the gate conductor is relatively high. While increasing the width of the gate conductor would also afford good conductivity of the gate conductor, it would undesirably lead to an increase in the threshold voltage, V.sub.T, of the transistor employing the gate conductor. Accordingly, in order to achieve good coverage of the vertically oriented sidewall surfaces of the gate conductor, an adequate amount of spacer material must be deposited across the gate conductor. Reducing the lateral thickness of the sidewall spacers thus cannot be achieved by decreasing the deposition time, and hence the thickness, of the spacer material. Moreover, the lateral thickness of the sidewall spacers cannot be reduced by increasing the anisotropic etch duration of the spacer material. That is, if the anisotropic etch is allowed to proceed too long, the gate conductor and the substrate will be over-etched, undesirably resulting in a significant decrease in the thicknesses of the gate conductor and the pre-existing LDD region within the substrate. In addition to preventing the reduction of the width of the LDD areas, this inability to reduce the lateral thickness of the spacers also limits the amount of packing density that can be achieved for an integrated circuit.
The dimensions of transistor features have become increasingly smaller to provide for faster, more complex integrated circuit devices. Unfortunately, the shrinkage of device dimensions has given rise to various problems. The distance between the source and drain regions of a transistor is often referred to as the physical channel length. However, after implantation of dopant species into the source and drain regions and subsequent diffusion of the dopant species, the actual distance between the source and drain regions becomes less than the physical channel length and is often referred to as the effective channel length ("Leff"). In VLSI designs, as the physical channel length becomes small, so too must the Leff. Decreasing the Leff of a transistor generally leads to so-called short-channel effects ("SCE") in which the transistor's properties, e.g., the transistor threshold voltage, undesirably vary from their design specification. Absent a comparable reduction in the depth of the source and drain junctions, the severity of the SCE resulting from a decrease in Leff may be profound. Accordingly, it has become necessary to scale down the vertical dimensions of the source and drain regions, (i.e., the depth of the source/drain implant), to ensure proper operation of transistor devices.
The formation of shallow source and drain regions (i.e., junctions) is, however, rather difficult for PMOSFET devices which include boron-implanted junctions. Due to the relatively high diffusivity and channeling of boron atoms, implanted boron can penetrate deeply into the substrate. While using very low implant energies of boron might produce relatively shallow junctions, advances in technology are required to make available low-energy ion implanters before such low implant energies can be realized. Further, while reducing the junction depth provides protection against SCE, it also gives rise to increased resistivity of the source and drain junctions, adversely impacting the device operation. As a result of the increased resistivity, the saturation drive current and the overall speed of the transistor may drop. Moreover, forming contacts to relatively shallow junctions has several drawbacks. A contact layer which consumes the underlying source and drain junctions is often used during contact formation. For example, a refractory metal may be deposited across the source and drain junctions and heated to promote a reaction between the metal and the underlying silicon, thereby forming a low resistivity self-aligned silicide (i.e., salicide) upon the junctions. The silicide may completely consume the shallow junctions, penetrating into the substrate underneath the junctions, a phenomenon known as "junction spiking", Consequently, the junctions may exhibit large current leakage or become electrically shorted. Therefore, precautions must be taken to prevent excessive consumption, and hence junction spiking, of the shallow junctions during contact formation.
It would therefore be of benefit to develop a technique for forming a transistor having LDD areas of relatively small width to afford a low resistance pathway between the source and drain junctions of the transistor. As such, the lateral thicknesses of sidewall spacers which dictate the lateral dimensions of the LDD areas must be reduced. Furthermore, the transistor design should call for relatively shallow "effective" source and drain junctions without being concerned that the resistivity of the junctions will be increased. Accordingly, the transistor design must account for reductions in the Leff of the transistor by providing protection against short channel effects. While reducing the effective depth of the source and drain junctions would be desirable, the actual depth of the junctions must be sufficiently large to avoid problems associated with junction spiking and excessive junction consumption.

Ultra thin spacers formed laterally adjacent a gate conductor recessed below the upper surface of a substrate


An image sensor includes a color filter array including a primary color pixel such as a green filter pixel for sensing a predetermined primary color, a first secondary color pixel such as a yellow filter pixel, and a second secondary color pixel such as a cyan filter pixel. The primary color pixel, the first secondary color pixel, and the second secondary color pixel form different area ratios in the color filter array. For example, the area ratio of the yellow filter pixel to the cyan filter pixel and the green filter pixel is 2:1:1 in the color filter array. In addition, the color filters of the pixels are compensated for crosstalk effect. Such an image sensor has enhanced color reproducibility and sensitivity.

This application claims priority under 35 USC §119 to Korean Patent Application No. 10-2007-0098900, filed on Oct. 1, 2007 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.
1. Field of the Invention
The present invention relates generally to image sensors, and more particularly to a color filter array for reducing crosstalk between pixels, an image sensor having the same, and an image pickup apparatus having the image sensor.
2. Background of the Invention
An image pickup apparatus includes a photo sensing device for converting light into electric signals. The image pickup apparatus is classified into a charge-coupled device (CCD) type and a CMOS image sensor (CIS) type depending on the kind of photo sensing device. The CIS type is currently used in many fields instead of the CCD type because of its characteristics of low-voltage operation, less power consumption, standard complimentary metal oxide semiconductor (CMOS) process and high integration as compared with the CCD type.
A CIS solid image pickup apparatus is installed in a portable camera, a digital still camera and the like to pick up images that are converted into electric signals that are transmitted to a digital signal processor. The digital signal processor performs signal processing on color image data (R, G, and B data) outputted from the CIS solid image pickup apparatus for driving a display apparatus such as a liquid crystal display (LCD).
Photo sensing devices generally sense only the intensity of received light and not the spectral characteristics. Thus, color filters are used for passing light frequencies in predetermined ranges to the photo sensing devices. Accordingly, respective color filters and photo sensing devices are used for a predetermined number of frequency ranges. As a result, the intensity of received light for each of the frequency ranges is determined for generating color image data (R (red), G (green) and B (blue) data).

Color filter array with reduced crosstalk effect and image sensor and image pickup apparatus having the same


An apparatus is disclosed for covering an electrical wall outlet and for maintaining the connection of electrical plugs thereto or to another electrical socket. The apparatus includes a cover plate presenting socket openings and at least one cap for housing a cord/plug assembly, the cap having a pair of legs with flanges attached to free ends thereof. The cover plate includes a pair of opposed slots about each socket opening, each slot having a first channel for receiving the appropriately aligned legs and flanges therein. A cap is secured to a cover plate by rotating the cap in a clockwise direction until the legs reach a terminal channel at which a portion of the plate overlies the flanges to preclude removal of the flanges from the channel. A cap is removable from the cover plate only by placing inward pressure on both legs while simultaneously rotating the cap for movement of the legs back to the first channel. The apparatus further includes a second cap similar to the first cap which includes a face plate having slots as in the cover plate. Each cap can house a cord/plug or socket assembly which can be locked together by inserting the legs of the first cap into the slots of the second as above described. As such ready access to the juncture of a socket/plug assembly of two wires is precluded. Alternatively, caps having completely closed ends may be engaged with the cover plate to cover an outlet socket which is not in use.

This invention relates to a device for covering electric outlets and, more particularly, to an apparatus which protects a young child from potential electric shock from an open outlet and prevents unintentional removal of an electrical plug from an outlet or another electrical plug.
Young children too frequently experience electrical shocks as a result of curiously placing their fingers or other objects into electrical outlets. Such shocks result in serious injury and sometimes, unfortunately, in death. A related problem is that electrical plugs often do not fit tightly into existing wall outlet receptacles, causing frequent disengagement of power to electrically powered devices when the plug falls out of the outlet. The inconvenience of power disengagement is also experienced when one power cord becomes loose or disconnected from a second cord such as an extension cord.
Several devices have been proposed which can either protect an individual from electric shock associated with a wall outlet, can prevent a power cord from unintentional removal from a wall outlet, or can prevent unintentional disengagement of the plug/socket juncture of two power cords. Although assumably effective in operation, such known devices are either complex in construction, difficult to use, or do not solve all of the problems described above.
For example, in U.S. Pat. No. 5,589,665 to Scamacca, an outlet cover is disclosed having a shell which protects a user from electric shock while preventing unintentional removal of a plug from a wall outlet. The shell, however, is secured to a special wall outlet through registration of a pin, slot, and aperture configuration which is not intuitive and is difficult to operate by persons unfamiliar with the device or who experience diminished dexterity. Further, a user is required to apply pressure to a specific location on the shell although a clear view of the attachment mechanism is not afforded.
Similarly, other known devices present relatively complex constructions or have attachment mechanisms which are not well suited for quick and easy attachment and removal by adult persons having limited dexterity. Also, it is desirable to have outlet cover apparatus which also houses and maintains the socket/plug connection between two electrical cords.
It is therefore desirable to have an apparatus which can protect young children from electric shocks caused by the insertion of fingers or other objects into an electrical outlet. It is also desirable to have an apparatus which prevents unintentional removal of a plug from an electrical outlet or from another socket at an end of an extension cord.

Electrical outlet safety cover and cord connector


A belt held retractor has a wire connected to a tubing that holds a carpenter""s pencil.

Carpenters and other skilled tradesmen frequently use a pencil to mark their work. In many cases, the user is on a scaffold, a ladder, or an elevated structure. There is a tendency to occasionally drop the pencil. Consequently, carpenters usually carry several pencils. It is inconvenient and costly to lose these special pencils.
The broad purpose of the present invention is to provide a retractable device for retaining a carpenter""s pencil or other writing instrument so that if the pencil is accidentally released, it does not drop to the ground. In the preferred embodiment of the invention, the carpenter uses a conventional, retractable reel such as is commonly used for keys and the like. The reel has a housing with a retainer that is clipped onto the user""s belt. It has a retractable spring attached to a key ring.
The carpenter""s pencil is connected to the key ring in one embodiment, by a relatively stiff expandable section of tubing. The tubing has a diameter less than that of a pencil. The user inserts the pencil into the tubing, expanding the tubing to form a tight frictional engagement with the pencil end. The other end of the tubing has a plug with a hole for receiving the key ring. The arrangement is such that if the carpenter should release the pencil, it is returned to the reel.
In another embodiment of the invention, the pencil is inserted in one end of the tubing to form a tight frictional engagement between the pencil and the tubing. The sides of the other end of the tubing are pressed together and formed with a hole, reinforced with the grommets, that forms an opening for the key ring.
In still another embodiment of the invention, when the user is employing a writing instrument other than the carpenter""s pencil, a section of tubing is employed that forms a frictional engagement with the end of the writing instrument. The other end of the tubing has a plug for receiving the key ring.
Still further objects and advantages of the invention will become readily apparent to those skilled in the art to which the invention pertains upon reference to the following detailed description.


A needle-less injector device that includes an outer housing and an inner housing that is slideably supported from the outer housing is disclosed. The inner housing supporting a vial that includes a nozzle for delivering a fluid held within the vial. A spring powered ram that is adapted for pushing a seal and plunger is mounted within inner housing. A skin tensioning spring mounted between the inner housing and the outer housing is used for pushing the leading end of the inner housing away from the outer housing. A trigger that cooperates with the spring-powered ram is used to release the ram from the cocked position only when the inner housing is in a firing position.

(a) Field of the Invention
This invention generally relates to a needle-less injector for delivering a dose of liquid into the inner housing of a human or animal. More particularly, but not by way of limitation, to a spring actuated needle-less injection device that delivers a high-pressure jet of fluid through the epidermis of the human or animal.
(b) Discussion of Known Art
The advantage of needle-less injection devices has been recognized for some time. Some of these advantages include the absence of a needle that presents a hazard to healthcare workers, the risk of cross-contamination between humans or animals is reduced, the risk of needle breakage in the tissue of the human or animal is eliminated, the jet is generally smaller than the diameter of a hypodermic needle and thus is less painful than a hypodermic needle.
Because of the well-known advantages of a needle-less injection device, there are many pneumatic or gas actuated needle-less injection devices that are designed to provide multiple doses to patients or animals. Most known needle-less injection devices operate by using a piston to drive the fluid to be delivered though a fine nozzle that creates a small, high pressure stream that penetrates the skin simply due to the high pressure. Multi-dose devices depend on a source of air or working fluid that is used to operate the piston that drives the fluid through the nozzle. Thus, a serious limitation of these devices is that they must have a readily available source of air or other fluid to drive the piston. This makes these devices impractical for use in the field conditions of remote areas and inconvenient in hospitals or clinics.
Because of the disadvantages of injection devices that use high-pressure fluids to drive the piston, a great deal of attention has been given to the development of a spring-powered needle-less injection device. The success of known devices has been limited, however, due to problems associated with safety and reliability. The issues regarding safety generally involve the possibility of accidental discharge of the device. And the problems of reliability generally involve the device's ability to deliver a full, known dose of the liquid being delivered into the animal or human.
Safety issues generally arise in association with devices that have exposed triggers or include a ram or piston driving device that can extend beyond the inner housing of the injector. The risk of using this type of device is similar to the risks associated with the triggers on firearms, and that is the inadvertent pressing of the trigger, causing the accidental or premature firing of the device.
Reliability issues include a broad spectrum of problems. One significant problem is the creation of a suitable jet or stream of fluid and the introduction of this jet on to the skin of the animal or human. Preferably, the jet will be a very fine jet that will impact a section of taught skin at an angle of incidence of preferably 90 degrees. Most of the energy of the stream is used to penetrate the skin when the jet impacts the skin at 90 degrees to the skin. Additionally, by keeping the skin taught prior to delivering the jet of fluid, the skin is not allowed to flex, an thus more of the energy from the jet is used to penetrate the skin rather than deflecting or moving the skin.
Therefore, a review of known devices reveals that there remains a need for a spring-operated injection device that prevents firing until the device is properly positioned against the skin.
There remains a need for a hand-held, spring operated needle-less injection device that will ensure that the skin is held taught and that the nozzle that is to deliver the jet is held at 90 degrees to the skin prior to allowing the jet to be delivered to the skin.

This patent is subject to a terminal disclaimer.


Reactive inks and methods of generating an image on a substrate using both reactive and heat activated inks are presented. An image is printed on a substrate, without reacting the reagents in the ink. Subsequently, the reagents are reacted to fix the image to a substrate, with substantial permanency and fastness. Sublimation or similar heat activated dyes are printed are also printed on the substrate. The sublimation or similar heat activated dyes are activated, and have an affinity for polymer that is applied to the substrate.

Known printing methods and processes for imaging substrates other than paper suffer from a lack of printing intensity and durability due to fibrillation problems. Images can be "washed out" through both the laundering and attrition of daily exposure of use, especially the substrates are textile or fabric materials. Fibrillation is a term that the textile industry used to describe small lint of fibers break loose from the fabric material and remain on to the very surface of the fabric or textile, resulting in a substantial decrease of color intensity. Fibrillation exists in knitted, woven, or non-woven fabric textile materials when natural fibers such as cellulose or modified cellulose fibrous are used at least as part of the fabric textile.
Pigments or dyes used in many printing processes are either opaque or are in a mixture of opaque binding materials. They provide good opacity, but a high level of image or color vividness is absent. This problem is heightened when cotton or similar natural fibers materials are used in the textile substrate, due to the opacity nature of the materials. Accordingly there remains a need for a digital printing process that provides permanent fixing of the image onto a fibrous natural or synthetic substrate, and provides good colorfastness, color vividness and color vibrancy, permanency and satisfactory 'hand'.
The use of computer technology allows substantially instantaneous printing of images. For example, video cameras or scanners may be used to capture a color image on a computer. Images created or stored on a computer may be printed on command, without regard to run size. The image may be printed onto substrates from the computer by any suitable printing means capable of printing in multiple colors, including mechanical thermal printers, ink jet printers and electrophotographic or electrostatic printers.


The systems, methods and apparatuses described herein provide a computing environment that manages application specific identification of devices. An apparatus according to the present disclosure may comprise a non-volatile storage storing identifier (ID) base data and a processor. The processor may be configured to validate a certificate of an application being executed on the apparatus. The certificate may contain a code signer ID for a code signer of the application. The processor may further be configured to receive a request for a unique ID of the application, generate the unique ID from the code signer ID and the ID base data and return the generated unique ID.

For many years, the processors within computing devices, such as laptops, smartphones or tablets, have used global identifiers (IDs) to uniquely identify the device to one or more applications running on the device. Sometimes the operating system will also have this type of global ID. When third-party applications are allowed to run within a computing environment, these applications, for a variety of legitimate reasons, typically request the IDs of the underlying hardware and/or operating system. For example, device-specific IDs may be used to combat fraud, authenticate access to beta versions of applications prior to their official release and power specific mobile advertising networks, among other reasons.
However, providing applications with a global identifier also poses significant and well-known privacy concerns. For example, global identifiers are sometimes used as authentication mechanisms for mobile networks, such as gaming networks. In such cases, if an attacker acquired a user's device-specific ID, the attacker may be able to access a multitude of other personal data, including information about a user's linked social networking site account(s), the user's email address(es) or the user's mobile phone number. Privacy concerns have caused such companies as Intel and Apple to discontinue the use of global IDs. For example, processors developed by Intel after the Pentium III family of processors have not supported processor serial numbers (PSN). As another example, Apple, Inc. began rejecting applications developed by third parties for the iOS platform that request a Unique Device Identifier (UDID).
At the present time, there is no technically and/or commercially viable method by which an application running on a computing device may have access only to its own application-specific ID and/or application-specific keypair. Currently available methods provide a single global ID for all applications, do not protect privacy from malicious applications, or rely on "security by obscurity" to enforce privacy.
What is needed are systems, methods and apparatuses for the secure, application-specific identification of devices that do not allow applications to access global device IDs or global public/private keypairs.

Systems, methods and apparatuses for the application-specific identification of devices


A superconducting dipole magnet structure that includes coil boxes, a dewar and a support device is provided, wherein each of the coil boxes is of a one-piece structure in which a superconducting coil is provided, wherein the superconducting coils are opposite to each other so that a uniform dipole magnetic field is generated when the two superconducting coils are energized, and wherein the support device is fixed to the dewar and supports the coil box in the way of point contact.

The medical technology of particle beam was developed from the United States in 1946 when Wilson firstly proposed particle beam treatment characteristics. There is a Bragg peak in particle beam. The Bragg peak can be adjusted to a tumor area through high-precision computer control technology, and large amounts of energy can be released. With the development of the medical technology of particle beam for half a century, particle therapy becomes a remarkable high and new technology for treatment of cancer because of its penetrating power, good dose distribution, less side scattering and other characteristics. With the continuous development of particle medical technology, heavy ion medical technology is also being developed continuously. In terms of beam type, heavy ions, especially carbon ions, are preferable because of their physical Bragg effect and special relative biological effect.
To achieve the particle and heavy ion medical treatment, the corresponding medical devices are needed. Considering the principle of structural composition, heavy ion and particle therapy systems are substantially the same, including accelerators, particle transport system, nozzle and treatment planning system. And with the rapid development of accelerator science, it has been difficult for conventional magnet accelerators to meet the requirements of various disciplines for high energy particle beam. Due to the high requirements of heavy ion and particle transporting for magnetic rigidity, the magnetic rigidity for deflecting heavy ion is 6.3 T·m and that for proton is 2.15 T·m, which makes it difficult to design the magnet used in the particle beam transport process because of the difficulty of achieving high strength magnetic field with traditional magnet. The only way for this is to increase the size of the magnet to meet the requirements, which makes the size and weight of existing transport system huge. As it is difficult for the conventional magnet to achieve electromagnetic field of high strength, the only way for this is to increase the radius of curvature to meet the requirements, which makes the existing gantry system huge and heavy. Especially for the last bending magnet, the weight of 90 degree bending magnet increases rapidly as the radius thereof increases. Taking Germany GSI HIT as an example, the weight of the 90-degree bending magnet is up to 90 tons, accounting for 65% of the weight of the entire gantry system. Excessive gantry weight will lead to severe deformation due to the uneven stress, thus affecting the isocentric error and rotation accuracy, hindering the wide application of ion beam medical treatment. The bending magnet is an important component of rotating gantry to realize the deflection function of iron beam and is an important factor for the size and weight of rotary gantry. Therefore, it is necessary to change the magnet structure and develop new magnet so as to overcome the defects of existing gantry of large size, high weight and high cost.

Superconducting dipole magnet structure for particle deflection

Hefei Institutes of Physical Science, Chinese Academy of Sciences


A method and apparatus are provided for servicing a customer of a builder by a third-party website provider. The method includes the steps of providing a first website by the third-party website provider for use by the customer in viewing and selecting product options for product offerings provided by the builder, receiving from the customer through the first website views and selections of an option of the options provided by the builder and collecting a fee or commission based upon the received selection made by the customer.

The invention relates to the construction industry and more particularly to methods of coordinating, displaying, processing and expediting selection processes of building options. The home-building business is used as a primary illustration, but this invention also applies to commercial, office, and other construction and renovation. Architects, designers, and renovators may find this invention useful, in addition to builders.
Construction is a very detail-oriented industry. Often a buyer or end-user (henceforth collectively referred to as "customer") and seller, builder, installer, or general contractor (henceforth collectively referred to as "builder") will meet many times to explore, select and negotiate overall scope and terms of a construction project. Often the only basis that a builder may have for quoting a price is a vague list or set of architectural drawings (layouts) and a general "sense" of what customers desire. In such cases, the builder may estimate the cost of "fitting out" a building based upon past experience or upon local trade craft for "typical" or "standards".
In the case of residential construction, a myriad of standard or above standard choices faces the customer once a contract has been signed. Often a builder will provide a number of options with regard to overall house design and functionality. Some options may relate to room and/or kitchen layout. A number of mechanical/system options, such as heating and cooling, may also be provided. Changes to a plan's electrical and plumbing systems, basement (either finished or unfinished), or garages may be available. Each option (or package of options) usually has its own advantages and disadvantages that may appeal to one customer over another.
Once the overall layout and functionality of a house is complete, the selection process may become even more involved. Design preferences such as floor coverings must be selected, kitchen and bathroom designs must be finalized. The customer must decide what color to paint the walls or whether wallpaper is a better choice.
The finalization of kitchen design is an especially complex process of integrating the various parts of design, products and "hook-up" of water, mechanical systesm, electric services, and other systems. Kitchen cabinets must be selected from any of a number of confusingly similar quantity, quality and feature options. Countertops, sinks and faucets must be coordinated to fit and function. Provision must be made for built-in appliances. Water, sewer and electric connections must be considered for each option. After cabinets have been selected, appliances may be ordered to conform to the overall design, or visa versa.
Bathroom choices are equally complex. Fixtures such as sinks, toilets, tubs and faucets must be selected. If the bathroom is to be tiled, then a type and color(s) must be selected to conform to the other choices.
Usually a builder provides an allowance for each option. The cheapest (or most popular) option may be included in the overall construction price. Where another option is selected, the customer may incur an additional charge or receive credit against the construction price, which must be included in calculations regarding credit, product installations and profit. The cost of labor expended in making design changes and installing options is another variable builders consider when pricing materials and substitutions, or offering credits.
While builders and customers may painstakingly track the customer selection process, the process requires countless hours spent presenting options and recording customer choices. Additional time is wasted relaying these various, interrelated choices to sub-contractors, vendors, distributors, manufacturers, purchasing managers, and job site personnel (henceforth collectively referred to as "trades"). Further, no true "retail" outlet exists for these options, essentially sub-trade industry products (i.e., faucets are available at plumbing supply showrooms, doors and trim at lumber yards, appliances at appliance stores). New construction products frequently vary from similar renovation products. Likewise, varied industry and non-trade pricing and discounts apply to these industry products.
Where the customer and builder have busy schedules, choices are often not made in a timely manner. Further, the Statute of Frauds requires a written note or memorandum (e.g., a signed contract, change order, etc.). Accordingly, a need exists for a means of facilitating the presentation and documentation process of products, services and processes of the construction industry.


Compounds of the formula (I) and salts thereof

Acylated aminophenylsulfonylureas, processes for their preparation and their use as herbicides and plant growth regulators.
The invention relates to the technical field of herbicides and plant growth regulators, in particular herbicides for selective combating of broad-leaved weeds and graminaceous weeds in crops of useful plants.
It is known that phenylsulfonylureas which are substituted by heterocyclic substituents and carry an amino or a functionalized amino group on the phenyl ring have herbicidal and plant growth regulating properties (EP-A-1515; EP-A-7687 (=U.S. Pat. No. 4,383,113); EP-A-30138 (=U.S. Pat. No. 4,394,506); U.S. Pat. No. 4,892,946; U.S. Pat. No. 4,981,509; EP-A-116518 (=U.S. Pat. No. 4,664,695, U.S. Pat. No. 4,632,695)).
Phenylsulfonylureas which contain, on the phenyl ring, a carboxyl group or a function derived from the carboxyl group in the 2-position and an N-alkyl-N-acyl-amino group in the 5-position have furthermore already been proposed in German Patent Application P 42 36 902.9 (WO-94/10154).
Surprisingly, it has now been found that certain phenylsulfonyl ureas which are substituted by heterocyclic substituents are particularly suitable as herbicides and plant growth regulators.
The present invention relates to compounds of the formula (I) and salts thereof
in which
W1 is an oxygen or sulfur atom,
W2 is an oxygen or sulfur atom,
n is 0, 1, 2 or 3, preferably 0 or 1, in particular 0,
R is halogen, alkyl or alkoxy, independently of other substituents R if n is greater than 1,
R1 is hydrogen or an unsubstituted or substituted hydrocarbon or hydrocarbonoxy radical,
R2 is hydrogen or an unsubstituted or substituted hydrocarbon radical,
or the group
NR1R2 is a heterocyclic ring having 3 to 8 ring atoms, which is unsubstituted or substituted and contains the N atom of the group NR1R2 as a hetero-ring atom and can also contain further hetero-ring atoms,
R3 is an acyl radical,
R4 is hydrogen or an aliphatic hydrocarbon radical,
X, Y independently of one another are halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, where each of the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, C1-C4-alkoxy and C1-C4-alkylthio, or are C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-alkenyloxy or C3-C6-alkynyloxy, and
Z is CH or N.
In formula (I) and in the formulae used below, the alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio radicals and the corresponding unsaturated and/or substituted radicals can be in each case straight-chain or branched in the carbon skeleton. If not stated specifically, the lower carbon skeletons, for example having 1 to 4 carbon atoms or, in the case of unsaturated groups, having 2 to 4 carbon atoms, are preferred for these radicals. Alkyl radicals, including those in the composite meanings, such as alkoxy, haloalkyl and the like, are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyl radicals, hexyl radicals, such as n-hexyl, i-hexyl and 1,3-dimethylbutyl, and heptyl radicals, such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals, and alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl; and alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl or 1-methylbut-3-yn-1-yl.
Halogen is, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl or alkynyl which are partly or completely substituted by halogen, preferably by fluorine, chlorine and/or bromine, in particular by fluorine or chlorine, for example CF3, CHF2, CH2F, CF3CF2, CH2FCHCl, CCl3, CHCl2 and CH2CH2Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 and OCH2CH2Cl; corresponding statements apply to haloalkenyl and other radicals substituted by halogen.
A hydrocarbon radical is a straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon radical, for example alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl, preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 5 or 6 ring atoms or phenyl; corresponding statements apply to a hydrocarbonoxy radical.
Aryl is a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl; aryloxy is preferably an oxy radical corresponding to the aryl radical mentioned, in particular phenoxy.
Heteroaryl or a heteroaromatic radical is a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, and also bicyclic or polycyclic aromatic or araliphatic compounds, for example quinolinyl, benzoxazolyl and the like. Heteroaryl also includes a heteroaromatic ring, which is preferably 5- or 6-membered and contains 1, 2 or 3 hetero-ring atoms, in particular from the group consisting of N, O and S. In the substituted case, the heteroaromatic ring can also be benzo-fused.
A heterocyclic radical or ring can be saturated, unsaturated or heteroaromatic; it contains one or more hetero-ring atoms, preferably from the group consisting of N, O and S; it is preferably 5- or 6-membered and contains 1, 2 or 3 hetero-ring atoms. The radical can be, for example, a heteroaromatic radical or ring as defined above, or is a partly hydrogenated radical, such as oxiranyl, pyrrolidyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl or tetrahydrofuryl. Possible substituents for a substituted heterocyclic radical are the substituents mentioned below, and in addition also oxo. The oxo group can also occur on the hetero-ring atoms which can exist at various oxidation levels, for example in the case of N and S.
Substituted radicals, such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heteroaryl, a substituted bicyclic radical or ring or a substituted bicyclic radical, if appropriate with aromatic moieties, are, for example, a substituted radical which is derived from the unsubstituted parent substance, in which the substituents are, for example, one or more, preferably 1, 2 or 3, radicals from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl, and the unsaturated aliphatic radicals corresponding to the saturated hydrocarbon-containing radicals mentioned, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy and the like. In the case of radicals with carbon atoms, those having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. Substituents from the group consisting of halogen, for example fluorine and chlorine, C1-C4-alkyl, preferably methyl or ethyl, C1-C4-haloalkyl, preferably trifluoromethyl, C1-C4-alkoxy, preferably methoxy or ethoxy, C1-C4-haloalkoxy, nitro and cyano are as a rule preferred. The substituents methyl, methoxy and chlorine are particularly preferred here.
Mono- or disubstituted amino is, for example, alkylamino, dialkylamino, acylamino, arylamino or N-aryl-N-alkylamino.
Optionally substituted phenyl is preferably phenyl which is unsubstituted or substituted once or several times, preferably up to three times by identical or different radicals from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyl 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl and o-, m- and p-methoxyphenyl.
An acyl radical is the radical of an organic acid, for example the radical of a carboxylic acid, and radicals of acids derived therefrom, such as thiocarboxylic acid or optionally N-substituted iminocarboxylic acids, or the radical of carbonic acid monoesters, optionally N-substituted carbamic acid, sulfonic acids, sulfinic acids, phosphonic acids, or phosphinic acids. Acyl is, for example, formyl, alkylcarbonyl, such as (C1-C4-alkyl)-carbonyl, phenylcarbonyl, in which the phenyl ring can be substituted, for example as indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and other radicals of organic acids.
The invention also relates to all the stereoisomers included by formula (I) and mixtures thereof. Such compounds of the formula (I) contain one or more asymmetric C atoms or also double bonds, which are not shown separately in the formula (I). The possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers and Z and E isomers, are all included by the formula (I) and can be obtained from mixtures of the stereoisomers by customary methods, or can otherwise be prepared by stereoselective reactions in combination with the use of stereochemically pure starting substances.
The compounds of the formula (I) can form salts in which the hydrogen of the xe2x80x94SO2xe2x80x94NH group or also other acidic hydrogen atoms (for example from COOH and the like) is replaced by a cation suitable for agriculture. These salts are, for example, metal salts, preferably alkali metal or alkaline earth metal salts, in particular sodium salts and potassium salts, or also ammonium salts or salts with organic amines. Salt formation can also be carried out by addition of an acid onto basic groups, such as, for example, amino and alkylamino. Suitable acids for this purpose are strong inorganic and organic acids, for example HCl, HBr, H2SO4 or HNO3. Compounds of the formula (I) according to the invention or salts thereof which are of particular interest are those in which
R1 is H or alkyl, alkenyl, alkynyl, alkoxy, alkenoxy, alkynoxy, cycloalkyl, cycloalkenyl or phenyl, where each of the nine radicals mentioned last is unsubstituted or substituted and contains a total of up to 24 carbon atoms, preferably up to a total of 12, in particular up to a total of 8 carbon atoms,
R2 is H or alkyl, alkenyl or alkynyl, where each of the three radicals mentioned last is unsubstituted or substituted and contains a total of up to 24 carbon atoms, preferably up to a total of 12 carbon atoms, in particular up to a total of 8 carbon atoms,
or the group
NR1R2 is an unsubstituted or substituted heterocyclic ring of four to eight ring atoms, where the group contains up to a total of 18 carbon atoms, preferably up to a total of 12 carbon atoms,
R3 is acyl having up to 24 carbon atoms, preferably up to 12 carbon atoms, in particular up to 8 carbon atoms, and
R4 is H or alkyl, alkenyl or alkynyl, where each of the 3 radicals mentioned last contains up to 12 carbon atoms, preferably up to 5 carbon atoms.
Compounds of the formula (I) according to the invention or salts thereof which are of particular interest are those in which
R1 is H, C1-C12-alkyl, C2-C12-alkenyl, C2-C12-alkynyl, C1-C12-alkoxy, C2-C12-alkenoxy, C2-C12-alkynoxy, C3-C8-cycloalkyl or C5-C8-cycloalkenyl, where each of the eight radicals mentioned last is unsubstituted or substituted, for example is substituted by one or more radicals from the group consisting of halogen, cyano, azido, COxe2x80x94R5, OR6, NR7R8, SR9, SOxe2x80x94R10 and SO2xe2x80x94R11, or unsubstituted or substituted phenyl,
is H, C1-C12-alkyl, C2-C12-alkenyl or C2-C12-alkynyl, where each of the three radicals mentioned last is unsubstituted or substituted, for example is substituted by one or more radicals from the group consisting of halogen, cyano, azido, COR12, OR13, NR14R15, SR16, SOxe2x80x94R17 and SO2xe2x80x94R18,
or the group
NR1R2 is a heterocyclic ring of four to eight ring atoms, which can contain up to two further hetero-ring atoms in the ring from the group consisting of N, O and S and is unsubstituted or substituted by one or more radicals from the group consisting of halogen, C1-C6-alkyl, NO2, N3 and CN,
R3 is COxe2x80x94R19, CSxe2x80x94R20, SO2xe2x80x94R21, SOxe2x80x94R21 or C(xe2x95x90NR21)xe2x80x94R19,
R4 is H, C1-C3-alkyl, C2-C5-alkenyl or C2-C5-alkynyl,
R5 is H, C1-C5-alkyl, C2-C5-alkenyl, C2-C5-alkynyl, C1-C5-alkoxy, C2-C5-alkenoxy, C2-C5-alkynoxy, NR22R23 or OH,
R6 is H, C1-C5-alkyl, C1-C5-haloalkyl, C2-C5-alkenyl, C2-C5-haloalkenyl, C2-C5-alkynyl or C2-C5-haloalkynyl,
R7 is H, C1-C5-alkyl, C2-C5-alkenyl, C2-C5-alkynyl, C1-C5-alkoxy, COxe2x80x94CH3, COxe2x80x94H or COOCH3,
R8 is H, C1-C5-alkyl, C2-C5-alkenyl or C2-C5-alkynyl or the group
NR7R8 is a heterocyclic ring of four to eight ring atoms, which can contain up to two further hetero-ring atoms in the ring from the group consisting of N, O and S and is unsubstituted or substituted by one or more radicals from the group consisting of halogen, C1-C6-alkyl, NO2, N3 and CN,
R9 is H, C1-C5-alkyl, C2-C5-alkenyl, C2-C5-alkynyl, C1-C5-haloalkyl, C2-C5-haloalkenyl or C2-C5-haloalkynyl,
R10 is C1-C5-alkyl, C2-C5-alkenyl, C2 -C5-alkynyl, C1-C5-haloalkyl, C2-C5-haloalkenyl or C2-C5-haloalkynyl,
R11 is C1-C5-alkyl, C2-C5-alkenyl, C2-C5-alkynyl, C1-C5-haloalkyl, C2-C5-haloalkenyl, C2-C5-haloalkynyl, C1-C5-alkoxyalkyl, C3-C8-cycloalkyl or C5-C8-cycloalkenyl,
R12 is a radical analogous to R5,
R13 is a radical analogous to R6,
R14 is a radical analogous to R7,
R15 is a radical analogous to R8, or the group
NR14R15 is a group analogous to NR7R8,
R16 is a radical analogous to R9,
R17 is a radical analogous to R10,
R18 is a radical analogous to R11,
R19 is H, C1-C12-alkyl, C2-C12-alkenyl, C2-C12-alkynyl, C1-C12-alkoxy, C1-C12-alkylthio, C2-C12-alkenoxy, C2-C12-alkynoxy, C3-C8-cycloalkyl, C5-C8-cycloalkenyl, C1-C12-alkylamino, di (C1-C6-alkyl) amino, Nxe2x80x94C1-C4-alkoxy-Nxe2x80x94C1-C4-alkylamino, where each of the 13 radicals mentioned last are unsubstituted or substituted, for example is substituted by one or more radicals from the group consisting of halogen, cyano, azido, COxe2x80x94R24, OR25, NR26R27, SR28, SOR29 and SO2R30, or an unsubstituted or substituted phenyl, phenoxy or phenylamino radical,
R20 is a radical analogous to R19,
R21 is a radical analogous to R11,
R22 is H, C1-C5-alkyl, C2-C5-alkenyl, C2 -C5-alkynyl, C1-C5-alkoxy, C2-C5-alkenoxy or C2-C5-alkynoxy, where each of the 6 radicals mentioned last is unsubstituted or substituted, for example is substituted by one or more radicals from the group consisting of halogen, cyano, azido, amino, mono- and disubstituted amino, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-alkylsulfonyl, C1-C3-alkylsulfinyl and C1-C3-alkylthio,
R23 is H, C1-C5-alkyl, C2-C5-alkenyl, C2-C5-alkynyl, C1-C5-alkoxy or C2-C5-alkenoxy, where each of the 5 radicals mentioned last is unsubstituted or substituted, for example is substituted by one or more radicals from the group consisting of halogen, cyano, azido, amino, mono- and disubstituted amino, C1-C3-alkoxy, C1-C3-alkylthio, C1-C3-alkylsulfonyl and C1-C3-alkylsulfinyl,
or the group
NR22R23 is a heterocyclic ring analogous to NR7R8, preferably a ring of 5 or 6 ring atoms, which can contain up to 2 further hetero-ring atoms in the ring from the group consisting of N, O and S and is unsubstituted or substituted by one or more radicals from the group consisting of halogen and C1-C4-alkyl,
R24 is H, C1-C3-alkyl, C1-C3-alkoxy, NH2 or mono- or disubstituted amino,
R25 is H, C1-C5-alkyl, C2-C5-alkenyl, C2-C5-alkynyl, C1-C5-haloalkyl, C2-C5-haloalkenyl or C2-C5-haloalkynyl,
R26 is H, C1-C3-alkyl, C1-C3-alkoxy, COxe2x80x94CH3 or COxe2x80x94H,
R27 is H, C1-C3-alkyl,
or the group
NR26R27 is a group analogous to NR22R23,
R28 is H, C1-C3-alkyl, C1-C3-haloalkyl, C2-C5-alkenyl, C2-C5-haloalkenyl, C2-C5-alkynyl or C2-C5-haloalkynyl,
R29 is C1-C5-alkyl, C1-C5-haloalkyl, C2-C5-alkenyl, C2-C5-haloalkyl, C2-C5-alkynyl or C2-C5-haloalkynyl,
R30 is analogous to R29,
W1 is O or S, preferably O,
W2 is O or S, preferably O,
X, Y independently of one another are halogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio, where each of the three radicals mentioned last is unsubstituted or substituted by one or more radicals from the group consisting of halogen, C1-C4-alkoxy and C1-C4-alkylthio, or are mono- or di(C1-C4-alkyl)amino, C3-C6-cycloalkyl, C3-C5-alkenyl or C3-C5-alkynyloxy, and
Z is CH or N.
Preferred compounds of the formula (I) according to the invention or salts thereof are those in which
R1 is H, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C2-C6-alkenoxy, C2-C6-alkynoxy or C5-C6-cycloalkyl, where each of the 7 radicals mentioned last is unsubstituted or substituted, by one or more radicals from the group consisting of halogen, cyano, azido, COxe2x80x94R5, OR6, NR7R8, SR9, SOxe2x80x94R10 and SO2xe2x80x94R11, or phenyl, which is unsubstituted or substituted by radicals from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy and nitro,
R2 is H, C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, where each of the three radicals mentioned last is unsubstituted or substituted by one or more radicals from the group consisting of halogen, cyano, azido, COR12, OR13, NR14R15, SR16, SOxe2x80x94R17 and SO2xe2x80x94R18,
or the group
NR1R2 is a heterocyclic ring of 5 or 6 ring atoms, which can contain up to two further hetero-ring atoms in the ring from the group consisting of N and O and is unsubstituted or substituted by one or more radicals from the group consisting of C1-C4-alkyl,
R3 is COxe2x80x94R19, CSxe2x80x94R20, SO2xe2x80x94R21 or C (xe2x95x90NR21)xe2x80x94R19,
R4 is H or CH3,
R5 is H, C1-C3-alkyl, C1-C3-alkoxy, NR22R23 or OH,
R6 is H, C1-C4-alkyl or C1-C4-haloalkyl,
R7 is H, C1-C3-alkyl, C1-C3-alkoxy, COxe2x80x94CH3, COxe2x80x94H or COOCH3,
R8 is H or C1-C3-alkyl,
or the group
NR7R8 is a heterocyclic ring of 5 or 6 ring atoms, which can contain up to two further hetero-ring atoms in the ring from the group consisting of N and O and is unsubstituted or substituted by one or more C1-C4-alkyl radicals,
R9 is H, C1-C3-alkyl or C1-C3-haloalkyl,
R10 is C1-C3-alkyl or C1-C3-haloalkyl,
R11 C1-C3-alkyl, C1-C3-haloalkyl, C1-C3-alkoxy-C1-C2-alkyl,
R12 is a radical analogous to R5,
R13 is a radical analogous to R6,
R14 is a radical analogous to R7,
R15 is a radical analogous to R8,
or the group
NR14R15 is a group analogous to NR7R8,
R16 is a radical analogous to R9,
R17 is a radical analogous to R10,
R18 is a radical analogous to R11,
R19 is H, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-alkylthio, C2-C6-alkenoxy, C2-C6-alkynoxy, C3-C6-cycloalkyl, C1-C6-alkylamino, di-(C1-C4-alkyl)amino or Nxe2x80x94C1-C4-alkoxy-Nxe2x80x94C1-C4-alkylamino, where each of the 11 radicals mentioned last is unsubstituted or substituted by one or more radicals from the group consisting of halogen, cyano, COxe2x80x94R24, OR25, NR26R27, SR28, SOR29 and SO2R30, or a phenyl, phenoxy or phenylamino radical, which is unsubstituted or substituted by radicals from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy and nitro,
R20 is a radical analogous to R19,
R21 is a radical analogous to R11,
R22 is H C1-C4-alkyl or C1-C4-alkoxy, where each of the 2 radicals mentioned last is unsubstituted or substituted by one or more radicals from the group consisting of halogen, cyano, amino, mono- and di-(C1-C4-alkyl)amino, C1-C3-alkoxy, C1-C3-alkylsulfonyl, and C1-C3-alkylthio,
R23 is H, C1-C5-alkyl, C2-C5-alkenyl, C2-C5-alkynyl, C1-C5-alkoxy or C2-C5-alkenoxy, where each of the 5 radicals mentioned last is unsubstituted or substituted, for example is substituted by one or more radicals from the group consisting of halogen, cyano, azido, amino, mono- and disubstituted amino, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-alkylthio, C1-C3-alkylsulfonyl and C1-C3-alkylsulfinyl,
or the group
NR22R23 is a group analogous to NR7R8,
R24 is H, C1-C3-alkyl, C1-C3-alkoxy, NH2 or mono- or di-(C1-C4-alkyl)amino,
R25 is H, C1-C5-alkyl or C1-C5-haloalkyl,
R26 is H or C1-C3-alkyl,
R27 is H or C1-C3-alkyl,
or the group
NR26R27 is a group analogous to NR22R23,
R28 is H or C1-C3-alkyl,
R29 is C1-C5-alkyl or C1-C5-haloalkyl,
R30 is analogous to R29,
W1 is O or S, preferably O,
W2 is O or S, preferably O,
one of the radicals X and Y is halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C4-alkylthio, where each of the three radicals mentioned last is unsubstituted or substituted by one or more radicals from the group consisting of halogen, C1-C2-alkoxy and C1-C2-alkylthio, or mono- or di(C1-C2-alkyl)amino, preferably halogen, methyl or methoxy, and the other of the radicals X and Y is C1-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy, C1-C2-haloalkoxy or C1-C2-alkylthio, preferably methyl or methoxy, and
Z is CH or N, preferably CH.
Particularly preferred compounds of the formula (I) according to the invention or salts thereof are those in which
R1 is H, C1-C2-alkyl, C1-C2-alkoxy or phenyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl and C1-C2-haloalkoxy,
R2 is H, C1-C2-alkyl or C1-C2-alkoxy,
or the group
NR1R2 is a heterocyclic ring of 5 or 6 ring atoms, which can contain up to one further hetero-ring atom in the ring from the group consisting of N and O and is unsubstituted or substituted by one or more C1-C2-alkyl radicals,
R3 is COxe2x80x94R19, CSxe2x80x94R20 or SO2xe2x80x94R21,
R4 is H or CH3,
R19 is H, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C4-alkylthio, C2-C4-alkenoxy, C2-C4-alkynoxy, C3-C6-cycloalkyl, C1-C4-alkylamino, di-(C1-C4-alkyl) amino, Nxe2x80x94C1-C2-alkoxy-Nxe2x80x94C1-C2-alkylamino, where each of the 10 radicals mentioned last is unsubstituted or substituted by one or more radicals from the group consisting of halogen and C1-C4-alkoxy, or a phenyl or phenoxy radical, which is unsubstituted or substituted by radicals from the group consisting of halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl and C1-C2-haloalkoxy,
R20 is a radical analogous to R19, and
R21 is C1-C3-alkyl, C1-C3-haloalkyl or C1-C3-alkoxy-C1-C2-alkyl.
Preferred compounds of the formula (I) according to the invention are those in which the group of the formula NHR3 on the phenyl radical is in the para-position to the group CW1xe2x80x94NR1R2 and in the meta-position to the SO2 group.
Preferred compounds of the formula (I) according to the invention are also those which contain a combination of the abovementioned radicals which are preferred in each case.
The present invention furthermore relates to processes for the preparation of the compounds of the formula (I) according to the invention or of salts thereof, which comprises
a) reacting a compound of the formula (II)
xe2x80x83with a heterocyclic carbamate of the formula (III),
xe2x80x83in which R* is unsubstituted or substituted phenyl or C1-C4-alkyl, or
b) reacting a sulfonyl isocyanate of the formula (IV)
xe2x80x83with a heterocyclic amine of the formula (V)
xe2x80x83or
c) reacting a sulfonyl chloride of the formula (VI)
xe2x80x83with a heterocyclic amine of the above formula (V) in the presence of a cyanate, for example an alkaline metal cyanate, such as sodium cyanate or potassium cyanate, or
d) reacting a sulfonamide of the above formula (II) with a (thio)isocyanate of the formula (VII)
xe2x80x83in the presence of a suitable base, such as, for example, potassium carbonate or triethylamine,
in which, in the above formulae (II) to (VII), the radicals R, R1, R2, R3, R4, W1, W2, X, Y and Z and the index n are as defined in formula (I), and where compounds of the formula (I) in which W2 is an oxygen atom are first obtained in variants a)-c).
The sulfonamides (II), the sulfonyl isocyanates (IV) and the sulfonyl chlorides (VI) are novel compounds. The invention likewise relates to these compounds and to their preparation.
The reaction of the compounds of the formula (II) and (III) is preferably carried out under base catalysis in inert solvents, such as, for example, methylene chloride, acetonitrile, dioxane or tetrahydrofuran, at temperatures from xe2x88x9210xc2x0 C. up to the boiling point of the particular solvent. Bases which are used here are, for example, organic amine bases, such as 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU), in particular in the case where R*=(substituted) phenyl (cf. EP-A-44807), or trimethyl- or triethylaluminium, the latter in particular in the case where R*=alkyl (cf. EP-A-166 516).
The compounds of the formula (II) are obtained, for example, from N-(t-butyl)-sulfonamides of the formulae (VIII), (IX) and (X) (cf. formula VIII*, Z*=R3NHxe2x80x94)
Starting from compounds of the formula (VIII) in which R, n, R1, R2, R3 and W1 are as defined in formula (I), compounds of the formula (II) are obtained by reaction with a strong acid. Possible strong acids are, for example, mineral acids, such as H2SO4 or HCl, or strong organic acids, such as trifluoroacetic acid. The t-butyl group is split off at temperatures of from xe2x88x9220xc2x0 C. to the particular reflux temperature of the reaction mixture, preferably at from 0xc2x0 C. to 40xc2x0 C. The reaction can be carried out in bulk or also in a solvent, such as, for example, methylene chloride or chloroform.
The compounds of the formula (VIII) are obtained, for example, from the aniline derivatives of the formula (IX) (cf. formula (VIII), R*=NH2) by reaction with suitable electrophiles, such as, for example, acid chlorides, acid anhydrides, isocyanates, thioisocyanates, sulfonyl chlorides or amidosulfonyl chlorides (in this context, cf.: A. L. J. Beckniter in J. Zabicky, xe2x80x9cThe Chemistry of Amidesxe2x80x9d, pages 73-185, Interscience, New York, 1970; E. J. Corey et al., Tetrahedron Lett. 1978, 1051; H. J. Saunders, R. J. Slocombe, Chem. Rev. 43, 203 (1948); S. Ozaki, Chem. Rev. 72, 457, 469 (1972); G. Zxc3x6lxcex2, Arzneim.-Forsch. 33, 2 (1983); Houben-Weyl-Hagemann, xe2x80x9cMethoden der organischen Chemiexe2x80x9d (Methods of organic chemistry), 4th edition, volume E4, page 485 et seq., Thieme Verlag Stuttgart, 1983; J. Golinsky, M. Mohasza, Synthesis 1978, 823; Houben-Weyl-Mxc3xcller xe2x80x9cMethoden der organischen Chemiexe2x80x9d (Methods of organic chemistry), 4th edition, volume IX, pages 338-400 and 605-622, Thieme Verlag Stuttgart, 1955; Houben-Weyl-Klarmann, xe2x80x9cMethoden der organischen Chemiexe2x80x9d (Methods of organic chemistry), 4th edition, volume E 11/2, pages 1020-22, Thieme Verlag Stuttgart, 1985; S. Krishnamurthey, Tetrahedron Lett. 23, 3315 (1982).).
The anilines (IX) mentioned are obtained by processes which are known from the literature, for example by reduction of the nitro groups from the compounds (X) (cf. formula (VIII), Z*=NO2), for example by catalytic hydrogenation or by reduction with iron in an acetic acid medium (in this context, cf.: H. Berrie, G. T. Neuhold, F. S. Spring, J. Chem. Soc. 1952, 2042; M. Freifelder, xe2x80x9cCatalytic Hydrogenation in Organic Synthesis: Procedures and Commentaryxe2x80x9d, J. Wiley and Sons, New York (1978), chapter 5).
The compounds of the formula (X) can be obtained by amidation, starting from the benzoates of the formula (XI):
The amide formation is carried out by reacting the benzoates (XI) (Rxc2x0=alkyl) with the amines of the formula (XII). The compounds of the formula (XI) and (XII) are starting materials which are known from the literature or commercially obtainable (cf., for example, German Patent Application P 42 36 902.9), or the compounds can be prepared analogously to generally known processes.
The amides of the formulae (VIII), (IX) and (X) are novel compounds. The invention likewise relates to these compounds and to their preparation.
The following synthesis sequence, which is explained below using the example of compounds where n=0, offers an alternative access to compounds (XI) (W1=0). Starting from 2-amino-nitrobenzoic acids (XIII), for example 2-amino-4-nitrobenzoic acid (XIIIa), the corresponding benzoic acid esters (XIV) (Rxc2x0=alkyl) are obtained by conventional esterification with the corresponding alcohols (Rxc2x0OH) and a suitable acid, such as, for example, H2SO4.
Diazotization of the amino group and subsequent reaction with SO2/CuCl2 gives the sulfonyl chloride (XV) (analogously to Meerwein, Chem. Ber. 90 (1957) 841-852).
Ammonolysis of compounds of the formula (XV) with t-butylamine leads to the sulfonamides of the formula (XI).
The carbamates of the formula (III) required for the reaction of the compounds (II) according to variant a) are known from the literature or can be prepared analogously to known processes (cf. EP-A-70 804 or U.S. Pat. No. 4,480,101).
The phenylsulfonyl isocyanates of the formula (IV) can be prepared, for example, analogously to the processes from EP-A-184 385 from compounds of the formula (II), for example with phosgene.
The reaction of the compounds (IV) with the aminoheterocyclic compounds of the formula (V) is preferably carried out in inert, aprotic solvents, such as, for example, dioxane, acetonitrile or tetrahydrofuran, at temperatures of between 0xc2x0 C. and the boiling point of the solvent.
The reaction of the sulfonyl chlorides (VI) with the amino-heterocyclic compounds of the formula (V) and cyanates, such as sodium cyanate and potassium cyanate, is carried out, for example, in aprotic solvents, such as, for example, acetonitrile, if appropriate in the presence of bases, for example 0.5 to 2 equivalents of base, or in basic aprotic solvents, at temperatures between xe2x88x9210xc2x0 C. and 100xc2x0 C., preferably xe2x88x9210xc2x0 C. and 60xc2x0 C., in particular at from 15xc2x0 C. to 40xc2x0 C. Possible bases or basic aprotic solvents are, for example, pyridine, picoline or lutidine or a mixture of these (cf. U.S. Pat. No. 5,157,119).
The (thio)isocyanates of the formula (VII) are obtainable by processes known from the literature (EP-A-232067, EP-A-166516). The reaction of the (thio)isocyanates (VII) with compounds (II) is carried out at from xe2x88x9210xc2x0 C. to 100xc2x0 C., preferably from 20 to 100xc2x0 C., in an inert aprotic solvent, such as, for example, acetone or acetonitrile, in the presence of a suitable base, for example N(C2H5)3 or K2CO3.
The salts of the compounds of the formula (I) are preferably prepared in inert solvents, such as, for example, water, methanol, acetone, methylene chloride, tetrahydrofuran, toluene or heptane, at temperatures of from 0 to 100xc2x0 C. Suitable bases for the preparation of the salts according to the invention are, for example, alkali metal carbonates, such as potassium carbonate, alkali metal and alkaline earth metal hydroxides, such as NaOH, KOH and Ca(OH)2, ammonia or a suitable amine base, such as triethylamine or ethanolamine. Suitable acids for the salt formation are, for example, HCl, HBr, H2SO4 or HNO3.
The xe2x80x9cinert solventsxe2x80x9d refer red to in the above process variants in each case mean solvents which are inert under the particular reaction conditions but are not required to be inert under any reaction conditions.
The compounds of the formula (I) according to the invention or salts thereof have an excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledon harmful plants. Perennial weeds which are difficult to combat and shoot from rhizomes, root stock or other permanent organs are also readily affected by the active compounds. it is irrelevant here whether the substances are applied prior to sowing, pre-emergence or post-emergence. Examples of some representatives of the mono- and dicotyledon weed flora which can be controlled by the compounds according to the invention may be mentioned specifically, without naming of these being intended as a limitation to particular species.
On the part of monocotyledon species of weeds, for example, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus species from the annual group and on the part of the perennial species Agropyron, Cynodon, Imperata and Sorghum and also persistent species of Cyperus are readily affected. In the case of dicotyledon species of weed, the action spectrum extends to species such as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the annual side and Convolvulus, Cirsium, Rumex and Artemisia among the perennial weeds.
Weeds which occur under the specific growing conditions in rice, such as, for example, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus, are also combated outstandingly by the active compounds according to the invention.
If the compounds according to the invention are applied to the soil surface before germination, either the emergence of the weed seedlings is prevented completely, or the weeds grow to the cotyledon stage but then stop growing, and finally die completely after three to four weeks have elapsed.
When the active compounds are applied to the green parts of plants by the post-emergence method, a drastic stop in growth likewise occurs very rapidly after the treatment, and the weed plants remain in the growth stage existing at the time of application or die completely after a certain period, so that weed competition which is harmful to crop plants is eliminated very early and lastingly in this manner.
Although the compounds according to the invention have an excellent herbicidal activity against mono- and dicotyledon weeds, crop plants of economically important crops, such as, for example, wheat, barley, rye, rice, maize, sugar beet, cotton and soya, are damaged only insignificantly or not at all. For these reasons, the present compounds are particularly suitable for selectively combating undesirable plant growth in agricultural crops of useful plants.
The substances according to the invention furthermore have outstanding growth regulatory properties in crop plants. They intervene by regulation in the endogenous plant metabolism and can therefore be used for specific influencing of plant contents and for facilitating harvesting, for example by inducing desiccation and compressed growth. They are furthermore also suitable for general control and inhibition of undesirable vegetative growth, without thereby killing the plants. Inhibition of vegetative growth plays a major role in many mono- and dicotyledon crops, since lodging can thereby be reduced or prevented completely.
The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the usual formulations. The invention therefore also relates to herbicidal and plant growth regulating compositions which comprise compounds of the formula (I) or salts thereof.
The compounds of the formula (I) or salts thereof can be formulated in various ways, depending on the biological and/or chemico-physical parameters which exist. Suitable formulation possibilities are, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), dressing compositions, granules for application by scattering and soil application, granules (GR) in the form of microgranules, spray granules, absorption granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
These individual types of formulation are known in principle and are described, for example, in: Winnacker-Kxc3xcchler, xe2x80x9cChemische Technologiexe2x80x9d (Chemical Technology), volume 7, C. Hauser Verlag Munich, 4th edition, 1986, Wade van Valkenburg, xe2x80x9cPesticide Formulationsxe2x80x9d, Marcel Dekker, N.Y., 1973; K. Martens, xe2x80x9cSpray Dryingxe2x80x9d Handbook, 3rd Edition 1979, G. Goodwin Ltd. London.
The necessary formulation auxiliaries, such as inert materials, surfactants, solvents and other additives, are likewise known and are described for example, in: Watkins, xe2x80x9cHandbook of Insecticide Dust Diluents and Carriersxe2x80x9d, 2nd Edition, Darland Books, Caldwell N.J., H.v. Olphen, xe2x80x9cIntroduction to Clay Colloid Chemistryxe2x80x9d; 2nd Edition, J. Wiley and Sons, N.Y.; C. Marsden, xe2x80x9cSolvents Guidexe2x80x9d; 2nd Edition, Interscience, N.Y. 1963; McCutcheon""s xe2x80x9cDetergents and Emulsifiers Annualxe2x80x9d, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, xe2x80x9cEncyclopedia of Surface Active Agentsxe2x80x9d, Chem. Publ. Co. Inc., N.Y. 1964; Schxc3x6nfeldt, xe2x80x9cGrenzflxc3xa4chenaktive xc3x84thylenoxidadduktexe2x80x9d (Surface-active ethylene oxide adducts), Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kxc3xcchler, xe2x80x9cChemische Technologiexe2x80x9d (Chemical Technology), volume 7, C. Hauser Verlag Munich, 4th Edition, 1986.
Combinations with other substances having a pesticidal action, such as, for example, insecticides, acaricides, other herbicides, fungicides, safeners, fertilizers and/or growth regulators, can also be prepared on the basis of these formulations, for example in the form of a finished formulation or as a tank mix.
Wettable powders are preparations which are uniformly dispersible in water and, in addition to the active compound, as well as a diluent or inert substance, also comprise surfactants of an ionic and/or nonionic nature (wetting agents, dispersing agents), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycolether-sulfates, alkane sulfonates, alkylbenzenesulfonates, the sodium salt of ligninsulfonic acid, the sodium salt of 2,2xe2x80x2-dinaphthylmethane-6,6xe2x80x2-disulfonic acid, the sodium salt of dibutylnaphthalene-sulfonate or also the sodium salt of oleoylmethyltaurine. To prepare the wettable powders, for example, the herbicidal active compounds are finely ground in customary apparatuses, such as hammer mills, blast mills and air jet mills, and mixed with the formulation auxiliaries at the same time or subsequently.
Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents, with addition of one or more surfactants of ionic and/or nonionic nature (emulsifiers). Emulsifiers which can be used are, for example: calcium salts of alkylarylsulfonic acids, such as Ca dodecylbenzenesulfonate, or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylarylpolyglycol ethers, fatty alcohol polyglycol ethers, propyleneoxide/ethyleneoxide condensation products, alkylpolyethers, sorbitan esters, such as, for example, sorbitan fatty acid esters, or polyoxyethylenesorbitan esters, such as, for example, polyoxyethylenesorbitan fatty acid esters.
Dusts are obtained by grinding the active compound with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
Suspension concentrates can be water- or oil-based. They can be prepared, for example, by wet grinding by means of commercially available bead mills and if appropriate addition of surfactants, such as have already been listed above, for example, for the other types of formulation.
Emulsions, for example oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and if appropriate surfactants, such as have already been listed above, for example, for the other types of formulation.
Granules can be fed either by spraying the active compound onto adsorbent, granular inert material or by application of active compound concentrates by means of adhesives, for example polyvinyl alcohol, the sodium salt of polyacrylic acid or mineral oils, to the surface of carriers, such as sand, kaolinites, or granular inert material. Suitable active compounds can also be granulated in the manner customary for the preparation of fertilizer granulesxe2x80x94if desired as a mixture with fertilizers.
Water-dispersible granules are as a rule prepared by the customary processes, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without a solid inert material.
The agrochemical formulations as a rule comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active compound of the formula (I) or salts thereof.
In wettable powders, the active compound concentration is, for example, about 10 to 90% by weight, the remainder to 100% by weight consisting of customary formulation constituents. In emulsifiable concentrates, the active compound concentration can be, for example, 1 to 90, preferably 5 to 80% by weight. Dust-like formulations comprise 1 to 30, preferably usually 5 to 20% by weight of active compound, and sprayable solutions comprise, for example, 0.05 to 80, preferably 2 to 50% by weight of active compound. In water-dispersible granules, the active compound content depends partly on whether the active compound is in liquid or solid form and which granulating auxiliaries, fillers and the like are used. In the case of granules which are dispersible in water, the content of active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
In addition, the active compound formulations mentioned comprise, where appropriate, the particular customary adhesives, wetting agents, dispersing agents, emulsifiers, penetration agents, preservatives, antifrost agents and solvents, fillers, carriers and dyestuffs, defoamers, evaporation inhibitors and agents which influence the pH and the viscosity.
Combination partners which can be employed for the active compounds according to the invention in mixture formulations or in a tank mix are, for example, known active compounds such as are described, for example, in Weed Research 26, 441-445 (1986), or xe2x80x9cThe Pesticide Manualxe2x80x9d, 9th edition, The British Crop Protection Council, 1990/91, Bracknell, England, and literature cited therein. The following active compounds are to be mentioned, for example, as herbicides which are known from the literature and can be combined with compounds of the formula (I) (Note: The compounds are designated either with their xe2x80x9ccommon namexe2x80x9d according to the International organization for Standardization (ISO) or by their chemical name, if appropriate together with a customary code number): acetochlor; acifluorfen; aclonifen; AKH 7088, i.e. [[[1-[5-[2-chloro-4-(trifluoromethyl)-phenoxy]-2-nitrophenyl]-2-methoxyethylidene]-amino]-oxy]-acetic acid and acetic acid methyl ester; alachlor; alloxydim; ametryn; amidosulfuron; amitrol; AMS, i.e. ammonium sulfamate; anilofos; asulam; atrazin; aziprotryn; barban; BAS 516 H, i.e. 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butralin; butylate; carbetamide; CDAA, i.e. 2-chloro-N,N-di-2-propenylacetamide; CDEC, i.e. diethyldithiocarbamic acid-2-chloroallylester; CGA 184927, i.e. 2-[4-[(5-chloro-3-fluoro-2-pyridinyl)-oxy]-phenoxy]-propanoic acid and 2-propynyl ester; chlomethoxyfen; chloramben; chlorazifop-butyl, pirifenop-butyl; chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal-dimethyl; chlorthiamid; cinmethylin; cinosulfuron; clethodim; clomazone; clomeprop; cloproxydim; clopyralid; cyanazine; cycloate; cycloxydim; cycluron; cyperquat; cyprazine; cyprazole; 2,4-DB; dalapon; desmedipham; desmetryn; di-allate; dicamba; dichlobenil; dichlorprop; diclofop-methyl; diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethazone, clomazon; dimethipin; dimetrasulfuron, cinosulfuron; dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 177, i.e. 5-cyano-1(1,1-dimethylethyl)-N-methyl-3H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate; F5231, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]-phenyl]-ethanesulfonamide; F6285, i.e. 1-[5-(N-methylsulfonyl)-amino-2,4-dichlorophenyl]-3-methyl-4-difluoromethyl-1,2,4-triazol-5-one; fenoprop; fenoxan, s. clomazon; fenoxaprop-ethyl; fenuron; flamprop-methyl; flazasulfuron; fluazifop and ester derivatives thereof; fluchloralin; flumetsulam; N-[2,6-difluorophenyl]-5-methyl-(1,2,4-triazolo-[1,5a]pyrimidine-2-sulfonamide; flumeturon; flumipropyn; fluorodifen; fluoroglycofenethyl; fluridone; flurochloridone; fluroxypyr; flurtamone; fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halosaten; haloxyfop and ester derivatives thereof; hexazinone; Hw 52, i.e. N-(2,3-dichlorophenyl)-4-ethoxymethoxy)benzamide; imazamethabenz-methyl; imazapyr; imazaquin; imazethamethapyr; imazethapyr; imazosulfuron; ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidid; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methyldymron; metobromuron; metolachlor; metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogensulfate; monolinuron; monuron; MT 128, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.e. N-[3-chloro-4-(1-methylethyl)-phenyl]-2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin; perfluidone; phenmedipham; phenisopham; phenmedipham; picloram; piperophos, piributicarb; pirifenop-butyl; pretilachlor; primisulfuronmethyl; procyazine; prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn; propachlor; propanil, propaquizafop and ester derivatives thereof; propazine, propham, propyzamide; prosulfalin, prosulfocarb; prynachlor; pyrazolinate, pyrazon; pyrazosulfuronethyl; pyrazoxyfen; pyridate; quinclorac; quinmerac; quinofop and ester derivatives thereof, quizalofop and ester derivatives thereof; quazalofop-ethyl; quizalofop-p-tefuryl; renriduron; dymron; S 275 i.e. 2-[4-chloro-2-fluoro-5-(2-propynyloxy)-phenyl]4,5,6,7-tetrahydro-2H-indazole; S 482, i.e. 2-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propynyl)-2H-1,4-benzoxazin-6-yl]-4,5,6,7-tetrahydro-1H-isoindole-1,3(2H)-dione; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, i.e. 2-[[7-[2-chloro-4-(trifluoromethyl)-phenoxy]-2-naphthyl]-oxy]-propanoic acid and its methyl ester; sulfometuron-methyl; sulfazuron; flazasulfuron; TCA; tebutam; tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, i.e. N,N-diethyl-3-[(2-ethyl-6-methylphenyl)-sulfonyl]-1H-1,2,4-triazole-1-carboxamide; thiazafluron, thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; trimeturon; vernolate; WL 110547, i.e. 5-phenoxy-1-[3-(trifluoromethyl)-phenyl]-1H-tetrazole.
For use, the formulations present in the commercially available form are diluted in the customary manner, if appropriate, for example by means of water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules, and then applied to the plants, parts of plants, or soil on which the plants are standing or in which they are growing or are present as seed and which is used agriculturally or industrially. Dust-like formulations, soil granules and granules for scattering as well as sprayable solutions are usually not additionally diluted with further inert substances before use.
The required amount of compounds of the formula (I) to be applied varies according to the external conditions, such as temperature, humidity and nature of herbicide used, inter alia. It can vary within wide limits, for example between 0.001 and 10.0 kg/ha or more of active substance, but is preferably between 0.005 and 5 kg/ha.

Abstract: in which W1, W2, R, n, R1, R2, R4, X, Y and Z are as defined in claim 1 and R3 is an acyl radical, are suitable as herbicides and plant growth regulators. The herbicides can be prepared by the process variants from claim 5, the novel intermediate products (II), (IV), (VI) and (VIII)* of claims 9 and 10 being employed.


A flooring support system comprising a floor having an upper surface and a lower surface, a base surface, a floor support for supporting the lower surface of the floor in spaced relation above the base surface, the support including a resiliently compressible body having a first end surface engaged with the lower surface of the floor, a second end surface facing opposite the first end surface and engaged with the base surface, a central portion located intermediate the first and second end surfaces, and pneumatic spring means in the central portion for storing energy transferred through the floor to the body and for returning to the floor from the body substantially all energy transferred to the body through the floor, the pneumatic spring including a mechanism for affording resilient deflection of the first end surface toward the second end surface and pneumatic air cells for resisting deflection of the first surface toward the second surface.

1. Technical Field
The invention relates generally to flooring systems, and particularly to flooring systems for providing a resilient surface.
2. Related Prior Art
Flooring systems for supporting a resilient floor or playing surface, e.g. a floor for athletic activity, such as basketball or gymnastics, or other physical activity, such as dancing, are known. One of the desirable characteristics of such flooring systems is the provision of a playing surface having superior traction. Another consideration in providing flooring system to support a resilient floor or playing surface, however, is the amount of resilient deflection or "give" provided by the floor in response to a downwardly directed force on the floor. This factor plays a significant role in determining the desirability of a particular flooring system.
In particular, it is undesirable for a flooring system to provide a playing surface which absorbs and dissipates a substantial amount of the energy transferred to the playing surface. Such a flooring system provides an undesirable "mushy" feel to those engaged in activity on the floor and tends to slow play. At the other extreme, it is also undesirable for a flooring system to provide a playing surface which does not adequately deflect in response to the force of an impact to the playing surface. Such a flooring system provides a playing surface without enough resilient deflection or "give", so that those engaging in activity on the playing surface receive the full shock of an impact on the playing surface.
In view of the foregoing, it is an object of the invention to provide a flooring system supporting firm and fast playing surface which resiliently deflects in response to the force of an impact on the playing surface.
Another object of the invention is to provide a flooring system supporting playing surface which resiliently responds to forces exerted on the playing surface and which subsequently returns to its original condition.


A protection device for a lens used in a scanning apparatus for imaging data on photographic film, comprises a plate and having a finger gripping portion, a member slidably retained in the plate, a glass piece removably carried by the member, and a biasing member operatively associated with the member for selectively permitting secure holding of the glass piece on the member and easy removal of the glass piece from the member. The plate is provided with a biasing device for securely retaining the member in a desired location such that the glass piece is in a predetermined lens protecting position. A switch is associated with the plate such that the switch is moved to an open position upon movement of the member away from the plate. The biasing member is a pivotally mounted spring configured to hold the glass piece in a desired location on the member and has V-shaped portions to engage portions of the member for positive locking of the spring in the member.

In the past, to the extent that lenses in photographic scanning apparatuses used protective covers at all, the covers were attached directly to the lens casing. This is particular problem in a scanning apparatus where the various components fit closely together and access thereto is not convenient. Moreover, it is relatively cumbersome process to remove a lens protector or cover in such a system, and this becomes a serious problem when the frequency of cleaning or replacement of the lens cover is fairly frequent. Consequently, the removal of the lens cover can also result in damage to other sensitive components.