A hammock tent comprises a ridgeline and a tent body attached to the ridgeline. The tent body comprises a platform, opposing sides, support structures, and opposing ends. The opposing sides are attached to first opposing edges of the platform. The support structures are attached to the opposing sides, and each comprise ends attached to the ridgeline and an apex proximate a central section of the platform. The opposing ends are positioned between the opposing sides, and are attached to edges of the opposing sides and second opposing edges of the platform. Additional hammock tent and a camping system are also described.

Conventional sleeping hammocks (e.g., hammock tents, camping hammocks, etc.) suffer from a number of design deficiencies. For example, many conventional sleeping hammocks provide a non-flat (e.g., curved) sleep surface, which can negatively affect user comfort and support. In addition, conventional sleeping hammocks providing a flat sleep surface (e.g., a level sleeping platform) may lack sufficient structure to provide durability, stability, and/or to adequately distribute tensional forces, resulting in sleeping hammocks that are unstable, uncomfortable, and/or prone to damage. Moreover, many conventional sleeping hammocks require precise hang angles for suspension equipment (e.g., ropes, straps, anchors, etc.) in order to reduce sag and achieve a flat sleep surface. The support structures employed by many conventional sleeping hammocks may also significantly affect the overall weight and/or profile of the sleeping hammocks, making the sleeping hammocks unappealing or impractical for many outdoor activities (e.g., backpacking). Furthermore, conventional sleeping hammocks having relatively reduced weight and/or profile often lack sufficient structural integrity and interior sleep for sustained, long-term use of the sleeping hammocks without sacrifices to durability, stability, and/or comfort.

Hammock tents and related camping systems


Crude fumed silica resulting from pyrogenic hydrolysis is purified by continuously feeding particulate silica and steam or a mixture of steam and air in a steam/air volume ratio of at least 1/2 through an upright column from its bottom toward its top for forming a fluidized bed within the column at a gas linear velocity of 1 to 10 cm/sec. and a temperature of 250.degree. to 400.degree. C., whereby steam deprives the particulate silica of the halide borne thereon, and removing fine particulate silica from which the halide has been eliminated from the top of the column. Using a simple apparatus, pure fine particulate silica is collected at a low cost of energy consumption.

1. Field of the Invention
This invention relates to a method for purifying fine particulate silica such as fumed silica by eliminating halide therefrom.
2. Prior Art
Fumed silica is widely used in the art as a filler for silicone elastomers and various other resins. In general, fumed silica is prepared by pyrogenic hydrolysis of silicon-containing halides. Since fumed silica has high surface activity and a large specific surface area, it has adsorbed thereon a substantial amount of hydrogen halide resulting from pyrogenic hydrolysis as a by-product. Fumed silica bears halogen in a chemically bonded state if the reaction is incomplete. It is undesirable to use fumed silica bearing a noticeable amount of halogen as a filler without treatment. Usually, such fumed silica is used after deacidifying treatment is carried out for eliminating the halide.
Conventionally, fumed silica is deacidified by using an endless steel belt or a rotary column with transfer means for bringing fumed silica in contact with wet air at 200.degree. to 500.degree. C. as disclosed in Japanese Patent Publication (JP-B) No. 46274/1972. Although deacidification can be done at relatively low temperatures, the apparatus includes mechanical movable parts which tend to fail during use in a hot acidic corrosive atmosphere.
Another known deacidifying method is countercurrent contact between fumed silica and wet air as disclosed in JP-B 13832/1973. Although this method avoids to place mechanical movable parts in a hot acidic corrosive atmosphere and allows for use of a relatively simple apparatus, the method is less efficient in that separation of coarse particles cannot be accomplished concurrently with the deacidification. The treating temperature is relatively high. JP-B 13832/1973 describes a comparative example using a parallel flow fluidized layer. It is described that this parallel flow fluidized layer is at a temperature of 600.degree. to 800.degree. C. Use of such high temperature is impractical because the material of the apparatus and the heat source are limited.

Method for porifying fine particulate silica


A prosthetic implant includes first, second and third components. The first component is configured to be disposed within the acetabulum. The second component is in a load bearing relationship with the first component, and is operable to rotate in a first axis of rotation. The second component is inhibited from movement in a second axis of rotation. The third component is in a load bearing relationship with the second component. The third component is operable to rotate in the second axis of rotation, but is inhibited from movement with the first axis of rotation.

Many orthopaedic procedures involve the implantation of prosthetic devices to replace badly damaged or diseased bone tissue. Common orthopaedic procedures that involve prosthetic devices include total or partial hip, knee and shoulder replacement. Hip replacement involves total or partial replacement of the hip ball and socket joint.
A total hip replacement procedure typically involves the implantation of two main component systems: the femoral component and an acetabular component. The femoral component includes a rigid stem that is anchored within the existing femur and also includes a head that replaces the natural hip joint femoral head. The acetabular component is secured within the acetabulum of the patient and serves as a bearing surface for the head of the femoral component.
Historically, acetabular components have a generally rounded outer surface that is secured to natural bone within the acetabulum and include a roughly hemispherical interior surface for receiving a round femoral head. The femoral head and hemispherical interior surface form a ball and socket joint that approximates the natural hip joint. The acetabular component often includes an outer shell and one or more intermediate components, or liners. The outer shell is anchored or otherwise secured to the bone tissue within the acetabulum and the liner or liners are disposed within the outer shell. The liner(s) form the bearing surface for the pivoting femoral head.
Regardless of the precise structure, prior art hip prostheses typically employ the ball and socket or spherical rotation joint to approximate anatomical hip movement.
A set of problems associated with hip prosthesis arises from the wear of the hip implant bearings. In particular, extensive use of a prosthetic hip can cause the bearings to wear, releasing debris in and around the surrounding tissue. For example, a typically total hip prosthesis includes a metal or ceramic outer shell, an ultra high molecular weight polyethylene (UHMWPE) liner, and a cobalt-chromium or ceramic femoral head. In such a prosthesis, it has been observed that the bearing surface of the UHMWPE liner wears, thereby producing particulate debris.
Particulate from UHMWPE wear can interfere with the motion capabilities of the prosthetic and furthermore can create an adverse biological reaction. Small debris can produce osteolysis (bone resorption) and/or cause an immune response.
Similarly, if a metal liner is instead used, the wear from the metal on metal bearings (metal liner to metal femoral head) can release increased levels of metal ions in the body which can produce adverse health effects. Ceramic liners do not produce metal ions, but are expensive and can fail in a brittle manner, which is highly undesirable.
Accordingly, there exists a need for reducing the adverse affects caused by wear of the bearing surfaces of total hip replacement prostheses.

Reduced wear orthopaedic implant apparatus and method


A parachute canopy system includes a canopy having a skirt and a suspension line system, where each suspension line of the suspension line system is attached to the skirt. A pair of first line members is attached to the canopy, the pair of first line members extending in a substantially radial direction away from the skirt towards a center of the canopy. A first end of each line member in the pair of first line members is connected together to the suspension line at the skirt. A first end of the second line member is connected to adjacent second ends of adjacent pairs of first line members that extend towards the center of the canopy.

Parachutes are commonly used to deliver cargo and supplies to area generally inaccessible by vehicle transport as well as to quickly supply military troops. Materials with high strength-to-weight ratios are standard for parachute design and construction.
Referring to FIG. 1, a plan view of a flat, circular parachute canopy system 100 of the prior art is illustrated. A typical parachute system 100 will include a canopy 112 that has a canopy skirt 108. The parachute system 100 will also include suspension lines 106 that are attached to the canopy 112 and a payload (not shown). Typical parachute canopies have suspension tapes 102 that radiate outward from the center 114 of the canopy 112. The canopy 100 includes radial suspension tapes 102 that are sewn or stitched to the canopy material 104. Attached to the suspension tapes 102 are the suspension lines 106 that support the payload (not shown). The suspension lines 106 are attached at the skirt 108 of the canopy material 104 at attachment points 110. While these suspension tapes 102 distribute the payload weight evenly over the canopy surface, they create stress in the canopy material 104. This can be evidenced by scalloping in the canopy material 104 when the parachute canopy 100 is inflated. It would be advantageous to be able to reduce the stress in the material of a parachute canopy 100 caused by the suspension tapes 102.
Accordingly, it would be desirable to provide a parachute canopy system that addresses at least some of the problems identified above.

Method of improved load distribution over the surface of a parachute canopy

The United States of America as represented by the Secretary of the Army


Aspects of the subject disclosure may include, for example, embodiments include obtaining video content, the video content comprises a plurality of frames, monitoring, by an image sensor, a facial feature of a user to determine a visual focus of the user in relation to the video content, and detecting from a group of frames of the plurality of frames at least a reduction in movements of objects in the group of frames. Further embodiments include determining, according to the monitoring and the detecting, a measure of attention of the user within a region of the group of frames, determining that the measure of attention of the user within the region of the group of frames satisfies a threshold, and embedding in at least a portion of subsequent frames of the plurality of frames a visual advertisement in the region via a communication device. Other embodiments are disclosed.

The current state of the art streams panoramic video content from a video server to a communication device communicatively coupled to a virtual reality headset to view the panoramic video content. Visual advertisements are provided by periodically interrupting the panoramic video content stream with one or more visual advertisements. Once, the visual advertisements are presented, the panoramic video content stream is resumed.

This patent is subject to a terminal disclaimer.

Methods, devices, and systems for embedding visual advertisements in video content


One or more of the embodiments described herein may include features related to the protection of chests, safes and other security enclosures and in particular to improvements to safes/chests and automatic banking machines which are subject to gas attack and similar assault which are perpetrated with a view to blowing up a chest to gain unauthorized access.

Automated banking machines may include a card reader that operates to read data from a bearer record such as a user card. The automated banking machine may operate to cause the data read from the card to be compared with other computer stored data related to the bearer. The machine operates in response to the comparison determining that the bearer is an authorized system user to carry out at least one transaction which is operative to transfer value to or from at least one account. A record of the transaction is also commonly printed through operation of the automated banking machine and provided to the user. A common type of automated banking machine used by consumers is an automated teller machine which enables customers to carry out banking transactions. Banking transactions carried out may include the dispensing of cash, the making of deposits, the transfer of funds between accounts and account balance inquiries. The types of banking transactions a customer can carry out are determined by the capabilities of the particular banking machine and the programming of the institution operating the machine.
Other types of automated banking machines may be operated by merchants to carry out commercial transactions. These transactions may include, for example, the acceptance of deposit bags, the receipt of checks or other financial instruments, the dispensing of rolled coin or other transactions required by merchants. Still other types of automated banking machines may be used by service providers in a transaction environment such as at a bank to carry out financial transactions. Such transactions may include for example, the counting and storage of currency notes or other financial instrument sheets, the dispensing of notes or other sheets, the imaging of checks or other financial instruments, and other types of service provider transactions. For purposes of this disclosure an automated banking machine or an automated teller machine shall be deemed to include any machine that may be used to electronically carry out transactions involving transfers of value.
Automated banking machines may benefit from improvements.
Overview of Example Embodiments
One or more of the embodiments described herein may include features related to the protection of chests, safes and other security enclosures and in particular to improvements to safes/chests and automatic banking machines which are subject to gas attack and similar assault which are perpetrated with a view to blowing up a chest to gain unauthorized access.
A vulnerability of chests, automated banking machines and the like to unauthorized entry and attack is a constant problem where the security of such chests is compromised by their physical exposure and position in the public domain. In addition to an array of physical attack, including drilling, angle grinders and the like, a recent development is an attack based on explosives where a combustible gas is injected into the interior of the chest or automated banking machine and the gas filled interior is subsequently ignited by remote electrical activation or other types of fusing. The generally sealed or air tight nature of such chests results in an explosive build-up of pressure from the ignition and the weakest point in the chest generally blows away giving access to the chest contents.
The incident of gas attack has become prevalent due to the relative ease of injecting LPG or other forms of volatile explosive gas including oxygen and acetylene into the card dispenser or insert slot of the automated banking machine. The slot also provides access for inserting a fuse or other ignition device and the closed, sealed nature of the automated banking machine provides a favorable environment to effect a substantial blast resulting in the destruction, of the chest or at least, the blowing off of the door or other component of the chest, thereby providing access to the contents thereof to the perpetrator.
In order to address the incident of gas attack, protective panels may be added including surround cages and the like to prevent the doors from being completely blasted off. In another protection strategy, inert gas may be provided to off-set and counteract the provision of combustible gas. In yet another attempt to counteract gas attack, exhaust gas fans and the like may be incorporated into automated banking machines with a view to drawing away a potentially combustible gas from the interior of a chest prior to ignition.
In another example embodiment a blast resistant and disbursement accessory may be mounted to a chest of an automated banking machine when the machine is manufactured or via retro-fitting to an existing chest of an automated banking machine or other security device. The accessory may comprise an auxiliary casing formed of blast resistant materials adapted for mounting to the body of a chest. The auxiliary casing may include an interior chamber to receive the explosive gasses generated by a blast. The auxiliary casing may also include one or a plurality of vent holes communicating with the interior chamber. In addition the auxiliary casing may include a sacrificial exterior vent door, adapted to deploy open and to dissipate explosive gasses applied to the interior of the chest. In addition the accessory may include a conduit to the interior chamber so that the exterior vent door is positioned remote from the vent holes so as to prevent direct access to the chest upon deployment.
The interior of the auxiliary casing may include one or a plurality of baffles. Also, the sacrificial vent door may be secured and lockable with the lock being adapted to open in response to the blast. In addition, vent holes may incorporate a fan, adapted to draw gasses from the interior of the chest to the interior chamber of said auxiliary casing. In a further example embodiment, an explosive gas detector may be positioned within the chest and an ignition device may be positioned within the interior chamber. Also, a spark arresting filter may be incorporated between the chest and the auxiliary casing to prevent flashback.
The lock may include a burst gate positioned between the interior chamber and the door to act as a throw bolt in the event of a blast conduited to the chamber. The blast gate may move between a resting closed position blocking the pathway between the chamber and the vent door to an open position providing a pathway between the chamber and the vent door. The vent door may also be held in a closed position by a sliding bolt. The sliding bolt may be moved by the blast gate responsive to a blast.


An x-ray imaging device may include a detector array and an x-ray converting layer coupled to the detector array. The detector array and the x-ray converting layer may be configured such that x-rays traverse the detector array before propagating in the x-ray converting layer. The x-ray imaging device may also include a buildup layer behind the x-ray converting layer. The x-ray imaging device may be used as a “universal” imager for both MV and kV imaging.

The outcomes of radiation therapy are often decided by the ability to deliver adequate dose to the tumor without also increasing dose to adjacent normal tissue which leads to unacceptable toxicity. For many patients, an effective strategy for increasing tumor dose is via stereotactic body radiotherapy (SBRT) and hypofractionated radiotherapy (HFRT). SBRT and HFRT may reduce the number of treatment sessions and enable better and more efficient cancer treatment. However, the application of SBRT and HFRT requires accurate patient setup and real-time image-based monitoring of patient/tumor position during treatment.
Dynamic adaptive radiotherapy (DART) opens a new era of cancer treatment. DART, as the name suggests, adapts dynamically to the ever-changing patient, and can adjust treatment delivery parameters in real time to correct for intrafractional motion and ensure that radiation is always aimed at the tumor rather than normal tissue. Application of DART also requires improved imaging for patient positioning and real-time tracking of the patient and tumor motion during treatment.
Radiation delivery machines such as LINACs have been equipped with electronic portal imaging devices (EPID) for acquisition of portal images to confirm patient setup. Existing EPIDs use megavoltage x-rays to provide 2D images but not 3D images. Further, existing MV imaging suffers from inferior image contrast and resolution, and requires higher dose than does kV imaging due to lower X-ray absorption of the devices at MV energies.
Accordingly, there is a need for electronic portal imaging devices capable of providing high-quality images using low-dose megavoltage x-rays. There is a need for imaging devices that are suitable for both kV and MV imaging and provides reliable 3D patient tracking in real time.


This invention relates to encapsulated flavor and/or fragrance preparations and a method for producing same from a spray solution consisting of an aqueous solution of polymeric carriers and emulsified flavors and/or fragrances. The granules have an adjustable particle size of between 0.2 and 2 mm, present even size distribution and a globular shape and are further characterized by a high concentration and high retention of volatile flavors.

Flavorings and perfumes are complex liquid mixtures generally of liquid components. Flavoring granules are required for different purposes. Flavoring encapsulation via spray-drying is customary, but in this only relatively fine and irregularly structured particles are produced (R. Buttiker, Dissertation ETH Zurich No. 6148).
An alternative to spray-drying is producing flavoring granules via fluidized-bed spray agglomeration. EP A 070 719 describes, for example, the production of flavoring granules in a conventional batch-operated fluidized bed. An emulsion of the flavorings to be granulated is sprayed into a fluidized bed which consists of air-fluidized particles. The particles then act as nuclei for the formation of the granule grains.
WO 97/16078 describes the production of flavoring granules in a conventional batch-operated fluidized-bed rotor granulator. The rotor granulator generates a vortexing of the fluidized bed present therein by means of a rotating base plate. In this process material can only be sprayed onto previously introduced cores, so that the flavoring content of the final product is very low.
Both processes operate batchwise, that is to say after processing a spray-solution batch, the production process is terminated and the granules are taken out of the apparatus. A new spray solution batch must then be processed. For reasons of economic efficiency, the processes must therefore be operated with high bed contents. For preset granule growth, a corresponding amount of spray solution must be evaporated. Therefore the high bed contents lead to long residence times of the granules which are in the range of hours. However, the long residence time with simultaneous heat stress of the granules in an air steam leads to correspondingly high losses in the volatile flavorings. Reducing air temperature and/or air throughput does not decrease the flavoring loss, since then, inevitably, the time for evaporating the spray solution is extended.
A further disadvantage of the process according to EP A 070 719 is that the products it produces must be rescreened to produce narrow particle size distributions. Firstly this is an additional labor cost, secondly valuable material is lost in the course of this.
A disadvantage in WO 97/16078 is the high proportion of filler in the granule core (approximately 60 to 90% by weight) and the adsorption of the flavorings to the granules which is only at the surface. The surface adsorption reduces the protection of the flavorings, limits the maximum loading and leads to undesirably high contents of flavorings of the surface of the granules.
Although the granules produced according to EP A 070 719 or WO 97/16078 can be provided with a coating in order to adjust the solubility and flavoring-release behavior, or to achieve a specific protective action, the still relatively non-uniform particle size distribution and the relatively irregular granule surface make uniform coating with constant coating thickness difficult. An actually time- or temperature-controlled release of the flavorings or perfumes can thus not be achieved.

Encapsulated flavor and/or fragrance preparations


An electrode (10) for performing an electrochemical treatment process has two cathode disks (35, 45) used as treatment locations for a component (55). By means of a return flow channel (23) formed parallel with the inflow bore (12), these two treatment locations are possible one behind the other, viewed in the axial direction of the electrode (10). Furthermore, the gaps (43, 45, 38, 39) located at both sides of the cathode disks (35, 45) have been embodied to be of different sizes. Together with the shape and the radius of the cathode disks (35, 45), contours with different sections are possible. The electrode (10) makes possible an economical production of components with specially shaped contours, and several contours in a single work step.

The invention relates to a device for the electrochemical treatment of recesses at the inside of components. With devices known so far, the electrolyte solution is introduced into a feed bore of the electrode and is passed along the treatment element of the electrode. The electrolyte solution flows back via a drain bore which has been cut aligned with the feed bore. Because of this the electrode is relatively long and can therefore only find limited use.

Device for electrochemically machining recesses


A file system (10) for a memory device includes a first volume (12), a second volume (14), and a third volume (16). The first volume (12) is located at a highest portion of the memory space defined by the file system (10) of the memory device and includes a primary volume and directory entry control block area (18) to store the control blocks associated with the entire memory space of the memory device. Control blocks are stored in a descending order within the first volume (12). The second volume (14) is located at an intermediate portion of the memory space defined by the file system (10) and includes a secondary volume and directory entry control block area (20) to store the control blocks when the primary control block area (18) of the first volume (12) is being erased and rewritten into. The third volume (16) is located at a lowest portion of the memory space defined by the file system (10) and is used to store data files in an ascending direction.

A flash eraseable programmable read only memory is a memory device containing many sectors and which is sector erasable and byte programmable. The memory device is typically divided into a plurality of volumes which are the unit eraseble quantity of memory on a given piece of hardware. A volume may be a single sector or multiple sectors of a storage space representing the capacity of the memory. Prior to writing to, or programming, a location within the memory device, the volume within which the location is found must be first erased and then the whole volume is rewritten to include the programmed location. Thus, programming of a single location requires an erase cycle of the volume within which the single location is located and a write time to rewrite the erased volume. Typical erase cycles take approximately one second to complete, an eternity to a computer system in processing information.
The erasing of a complete volume every time a location is programmed occurs due to a file system of the memory device. The file system of a memory device determines the arrangement of data files within the memory space of the memory device. Operations with respect to the file system include formatting the file system and creating, writing, reading, appending to, and deleting data files. A data file may have associated with it a directory entry and a volume entry that reside in the memory device as control blocks. The directory entry describes aspects and attributes of the associated data file and the volume entry describes the underlying technology of the memory device. Typically, the control blocks for the directory entry and volume entry of an associated data file are stored within the same volume as the associated data file in accordance with the file system of the memory device. Such file system structure leads to time consuming erasure and rewriting of entire volumes of the memory device even though only a single location may be programmed. Therefore, it is desirable to have a memory device which does not require a lengthy erasure of an entire volume when programming a single location within memory device.

Flash memory file system for writing data files without rewriting an entire volume


A lead sheath assembly, including a lead sheath; a plurality of external wires; a jumper box; and a connecting terminal. The lead sheath includes a cavity. The jumper box includes: a plurality of through holes, a front end including a front interface, and a rear end including a rear interface. The external wires are mounted on the lead sheath. The jumper box is disposed in the cavity. The connecting terminal is disposed in the through hole.

Field of the Invention
The invention relates to a lead sheath assembly and a motor comprising the same.
Description of the Related Art
A typical lead sheath assembly for a motor includes a lead sheath and a connector. The connector is mounted in a cavity of the connector. One end of the connector is connected to a control board arranged inside the motor, and the other end of the connector is connected to an external application via a leading wire. However, the assembly has the following problems: 1) when the functions of the motor needs to switch, it requires to connect to the external application via the connector, and the function switch of the motor can only be realized by externally inputting a control command. Thus, the assembly is complicate, the use is troublesome, and the reliability is low. 2) The connector is unstably installed on the lead sheath and is easily loose, thereby resulting in hidden danger. 3) The connector has no protective measurements in nonuse state, and the port of the connector is easily polluted or damaged, which may decrease the stability and the safety of the connector in the use state. The same problems also exist in the motor using such a lead sheath assembly.

Lead sheath assembly and motor comprising the same


A method for defining a group from among a plurality of bidirectional objects, comprising the following stages: a) synchronous application to the objects in a group of an initiator event, b) sending of a message containing a group identifier, and c) recording by the objects that have been subjected to the initiator event of the group identifier.

Such home automation systems are used for motorized products or automatic devices for closing or solar protection in the building, or for the control of lamps or other systems. Typically, one or more command transmitters are provided; each device to be controlled—rolling shutter, blind, lighting unit, etc.—is associated with a command receiver; it is also possible for provision to be made for several devices to be controlled by a same command receiver. The command transmitters and command receivers communicate by radio and use the same transmission frequency, or predetermined frequencies. For these devices, and in particular for motorized products or automatic devices for closing or solar protection in buildings, logistic reasons most often necessitate that the pairing is not performed during manufacture, but rather on the worksite, after installation of the products. Various pairing solutions are proposed in the state of the art.
Certain solutions relate the case where command transmitters are capable only of transmitting and where command receivers are capable only of receiving. U.S. Pat. No. 4,750,118 or U.S. Pat. No. 6,049,289 are examples of such solutions. Other solutions use command transmitters and command emitters capable of transmitting and receiving; U.S. Pat. No. 4,529,980, or U.S. Pat. No. 5,148,159 are cited in particular.
French patent application FR-A-2 827 414, published after the priority date of this application, describes a method of pairing transmitter and receiver. In this application, it is proposed to fit the receiver with a hardware or software device to set it to pairing, or learning, mode. When said device is active, the receiver moves into pairing mode. When it ceases to be active, the receiver reverts to operational mode. The device can be sensitive to a momentary cut in the receiver power supply.
Moreover, a method of re-initialising a rolling shutter operator using an additional wire, which may be connected to the mains, is known. Such a solution is described in FR-A-2 808 834.
U.S. Pat. No. 6,028,866 describes a communication system in which each device includes a communication identification, which is allocated in the factory or by the user. For a group constitution, a central device sends a message inviting devices to join the group. On receipt of an invitation message, a device responds as appropriate with an acceptance message. The central device stores a list of the devices forming the group, i.e. the devices that have responded with an acceptance message. Said procedure for forming a group allows messages intended for the group to be sent.
EP-A-0 651 119 describes a set of transmitters and receivers, and mentions the pairing problem. Pairing is effected by learning a code for one transmitter from another transmitter. The two transmitters are placed side by side and the button for the channel in question is pressed on each transmitter, starting with the "teaching" transmitter. This gradual method of learning the codes is also applied to the receiver. The document envisages inhibiting the code teaching function on some transmitters. This document does not propose to form groups from among receivers.
WO-A-01 71685 discloses a universal remote controller, suited to controlling various units. Each unit contains a record of the various data necessary to allow the controller to manage it remotely, with a device code in particular; the record is copied into the universal controller. This document proposes that the controller interrogates the various units that it controls successively. It is proposed to group in a network the different units controlled by a remote controller; WO-A-01 71685 does not give details of how to form such a network.
U.S. Pat. No. 5,797,085 describes a communication system in which the different objects are not paired. On the contrary, the objects are identical from the communication point of view and do not have an unique address.
There is always a requirement for a method of defining a group from among a plurality of operators simply and reliably. Such a process must maintain its reliability even in a dense radio environment or heavily loaded network—for example in the presence of previously configured neighbouring products, or neighbouring products undergoing configuration.

Method for defining a group from among bi-directional objects


A device, particularly for compensating the internal and external pressures in a double-glazing unit, such double-glazing units comprising a frame which supports two sheets made of at least partially transparent material, a chamber being formed between the two sheets and being adapted to provide an air space for thermal and acoustic insulation. The device comprises a duct which connects the inside of the chamber to the outside environment and is shaped so as to form two siphons arranged in series, a first siphon, located towards the chamber, having a higher head than a second siphon, located towards the outlet of the duct into the outside environment, the device further comprising elements for absorbing the moisture of the air contained in the portion of duct between the siphons.

The present invention relates to a device which is particularly but not exclusively useful for compensating the internal and external pressures in double-glazing units.
Conventional double-glazing units are becoming increasingly widespread in the field of constructions, as well as in other fields, said double-glazing units being particularly appreciated because of their thermal and acoustic insulation features.
All currently commercially available double-glazing units have a substantially common structure despite the variety of their embodiments.
In particular, a double-glazing unit is constituted by a frame which supports two sheets of an at least partially transparent material, between which a chamber is provided which is adapted to form an air space for thermal and acoustic insulation.
This air space, usually filled with isolated air, gives double-glazing units their particular characteristics.
In some particularly advanced double-glazing units, means for blocking sun rays, such as for example blinds, roll-up shutters, Venetian blinds, or others can slide inside the chamber formed by the sheets.
In double-glazing units, one of the two sheets is normally exposed to the outside environment whilst the other one is exposed to the inside environment of the building.
This arrangement of double-glazing units causes them to be in contact with temperatures which are sometimes considerably different from each other.
Moreover, as known, the temperature increases inside the double-glazing unit due to the greenhouse effect when it is struck by the sun rays, indeed because some of the rays are captured and reflected several times between the facing inner and outer surfaces of the two sheets.
These behaviors cause a difference in temperature and especially in pressure between the air inside the chamber formed by the two sheets and the outside pressures.
This pressure gradient causes a significant deformation of the sheets which leads to many drawbacks.
Among these drawbacks, the generation of reflections, which are particularly unpleasant and sometimes dangerous for people outside the building, should be mentioned in the case of reflective sheets for outdoor use.
Another drawback, particularly for double-glazing units in which sliding blocking means are inserted, is the reduction in the functionality of said means, which are prevented from sliding smoothly by the sheet deformations.
Sometimes, in cases in which the deformation of the sheets becomes particularly significant, the darkening means are fully prevented from sliding, thus completely losing their functionality.
In order to eliminate this drawback, valve means have been conceived for compensating the internal and external pressures; however, said means have not yielded satisfactory results, since they exhibit a certain delay in their compensating response when the pressure gradient occurs and increases and also because any air drawn from the outside has a certain moisture degree which is particularly harmful inside the double-glazing unit.
In addition to applying valve means, it is therefore necessary to provide, for this purpose, moisture absorbing means such as hygroscopic salts, which however must also be replaced appropriately, since they quickly saturate, especially in very moist environments.
Another compensation method has been obtained by providing deformation-absorbing regions constituted by membranes made of an elastic material.
In this case, too, the compensating response of the membranes is not ideal, since said membranes move when the pressure gradient is already too high and therefore the sheet is already deformed.

Device, particularly for compensating the internal and external pressures in a double-glazing unit


A shirt box suitable for receiving a shirt includes a base, a box cover and a transparent protective member (insert). The base has a floor and a plurality of upstanding walls that define an interior compartment and the box cover has a top wall and a plurality of walls that surround the top wall (e.g., around a peripheral edge thereof). The top surface has a first opening formed therein that is formed at a location that permits a consumer to see the shirt or other item that is contained within the box. The transparent protective member (insert) has a top surface and a plurality of peripheral walls that surround the top surface (e.g., around a peripheral edge thereof) so as to define a structure that is free standing and independent from both the base and the cover.

In the retail sale of dress shirts and dress shirts and tie combinations, it is desirable to present the merchandise in a manner that permits potential customers to have a good look at the product. On the other hand, it is important for retailers to keep the product clean and free of any soil or stains that may result from handling, to protect against theft, and to maintain the shirts in an orderly and well-folded condition so that their displays remains attractive to passers by.
It is also desirable to have a packaging that addresses the foregoing needs and which permits shirts to be stacked in great number to promote efficient shelf and display space usage.
The present invention satisfies these and other needs.


The receiving antenna comprises at least two sectors or sections of paraboloids focusing the radiation onto their axes at points F.sub.1 and F.sub.2 respectively offset by a whole number of wavelengths of the received radiation. Each sector or section is associated with a helicoidal source located in its focal zone and having the same axis as that of the corresponding sector.

The antenna of a satellite receiving station is conventionally constituted by a parabolic reflector. This reflector is most often of circular or ovoid shape. In all cases, the reception principle remains the same: the electromagnetic waves are focused onto the reception focus. The signal is received by a "source" and then amplified by the microwave frequency head.
There are several types of parabolic antennas. The three main types of antennas are as follows:
The antenna of the type having symmetry of revolution, or the "Prime focus" type whose microwave frequency head is supported by a tripod fixed to the outer edges of the parabola, and directly placed in the proximity of the focus of the reflector: the presence of the head in the active part of the parabola results in a masking effect and in diffraction phenomena. A waveguide (feeder) is sometimes used to convey the signal from the source to the microwave frequency head (placed at the rear in this case). PA1 The "Cassegrain" type antenna whose microwave frequency head is installed at the rear of the main reflector and receives the waves reflected on a hyperbolic sub-reflector which reconcentrates the signals received by the main reflector towards the low noise amplifier (called LNA "Low Noise Amplifier"); this sub-reflector is the generator of a masking effect. PA1 The antenna of the offset illumination type which is a parabolic antenna having an off centered focus: the low noise amplifier and the source are offset in such a way as to reduce the masking effect. PA1 the receiving gain of a flat antenna is on average 25% lower than that of a parabolic antenna, the bandwidth is limited and in order to receive the 2 circular polarisations, 2 antennas are necessary; PA1 the production cost of such an antenna is high, principally for two reasons: PA1 1. expensive materials are necessary in order to minimise losses; PA1 2. the matrix represented by the receiving area of the antenna requires an individual connection of each of the microelements. PA1 right circular polarization (or "right hand circular polarisation") for example TDF1, BSB, BS, OLYMPUS; PA1 left circular polarization (or "left hand circular polarization") for example TVSAT, OLYMPUS. PA1 horizontal linear polarisation: for example Intelsat V, ECS 1 F1 PA1 vertical linear polarization: for example Intelsat V, ECS 1 F1, Telecom 1; the channels of the satellites of the "Eutelsat" and "Intelsat" organizations allocated to television transmissions are divided into two sub-groups of programmes, each of which corresponds to a different polarization.
The choice of the type of antenna principally depends on the size of the microwave frequency head used: a voluminous microwave frequency head, if it is placed at the center of the parabola, reduces its gain. Furthermore, the materials used for constructing parabolic reflectors are principally of the plastic or metallic (aluminium) type. Finally, the diameter of the parabola is a function of the merit factor, G/T, linking the gain G of the parabola and the overall noise temperature (T) desired on the station. This diameter has been able to decrease considerably in recent years, with a constant G/T, because of technological improvements in the amplifiers which result in a reduction of their noise temperature. The diameter of the parabola defines its beam width and, in addition to their discretion, the major advantage of parabolas of small diameter is the ease of aiming because of the corresponding increase in beam width. However, at the same time, the beam width determines the sensitivity of the system to interference coming from satellites adjacent to the satellite aimed at, which limits the possible reduction in diameter.
Furthermore, most manufacturers are currently developing array antennas, called flat antennas, intended either for receiving television transmissions, or for communications, mobile or fixed, for data transmission for professional use: the entire area of the antenna receives the radio signals transmitted by the satellite; an array of receiving microelements is placed in parallel and the gain is a function of the area of the antenna.
The efficiency of such flat antennas reduces considerably when the antenna area increases because of the loss generated in the summing systems.
But, the use of a flat antenna is capable of simplifying the procedures and therefore of limiting the costs of installations: a flat antenna can be installed almost vertically on a wall, or stuck to a roof. It merges with the decor (greater aesthetic qualities given it by its design): small thickness, reduced dimensions (it is configured in the form of squares of side 35 to 70 cm), lightness, discretion;
In order to be capable of receiving programmes from several satellites a flat antenna should be motorised. Array antennas with electronic aiming are being developed. They will allow the reception of transmissions from several adjacent satellites without movement. But no production for the general public is known at present as each microelement must be controlled in phase which considerably affects the gain and the noise temperature of the antenna.
Furthermore, in the current state of the art, these flat antennas have three big disadvantages:
With regard to the microwave frequency heads, these are composed of two elements: a low noise amplifier (LNA) and a low noise converter (LNC for Low Noise Converter), which can be connected as independent modulators one after the other, or integrated in a single block (LNB: Low Noise Block down converter).
Furthermore, the frequency bands allocated to television transmissions by geostationary satellite have been optimized to release a sufficient number of channels for all potential users (countries and international organizations). Consequently, satellites of the DBS type use two types of electromagnetic radiation polarized in opposite directions. Two transmissions can thus coexist on a same channel: their opposite polarizations enable them to be separated on reception.
The polarisations used by the two types of television satellites are as follows.
For direct television broadcast satellites:
For telecommunications satellites:
When a receiving station is intended to receive several types of polarizations, depolarizers are provided in order to allow the user to choose the desired polarization at will. The choice of these systems depends on the nature of the polarizations received.
In the case of horizontal and vertical polarisations, it is necessary to have recourse to a motorized polarization changing system, most often mounted on the waveguide of the parabola.
In the case of right and left circular polarizations (direct television broadcast satellites), the simultaneous reception of polarized signals requires a double output waveguide, equipped with an orthomode transducer allowing the mounting on a same parabola of two microwave frequency heads each dedicated to a different polarization.
Motorized systems intended to ensure the switching of the microwave frequency heads at the center of the parabola are now developed, but the reliability of these equipments is insufficient.
Very wide band heads, which are multi-frequency by band switching or agile frequency synthesis, should allow the reception of all of the frequencies allocated to television transmissions. But such multi-band heads will not quickly be available at reasonable prices.
The output of the microwave frequency head is connected to a demodulator which converts and demodulates the signal received in the satellite intermediate band (BIS) 950 to 1750 MHz. The demodulator allows the selection of the satellite channels to be carried out. Only demodulators having a very wide input band, which cover the entire frequency range from 950 to 1750 MHz, are capable of receiving the transmissions from all of the satellites which will cover Europe in the coming years. At present, these demodulators are only used to the maximum of their capabilities in motorized stations intended for the reception of several satellites.

Multifocal receiving antenna with a single aiming direction for several satellites

Thomson-LGT Laboratoire General des Telecommunications


Membrane filtration assembly where the fluid to be filtered is recirculated on the retentate side of a membrane filter and where the filtered fluid, i.e. the permeate, is recirculated on the permeate side of the membrane filter in such a manner that the two streams are cocurrently passed along the membrane filter. The membrane filter comprises several membrane units in form of tubular supporting structures, each supporting structure comprising one or more filter membranes. The membrane units are mounted in parallel inside a common housing in such a manner that one stream flows inside the membrane units while the other stream flows in a space surrounding said membrane units. Each membrane unit is provided with a separate space designed as a narrow passageway on the inner side defined by the membrane unit and on the outer side defined by a channel tube, the inner cross section of which is 4 to 200% larger than the outer cross section of the membrane unit. The assembly is easy to clean, and it is easy to replace the individual membrane units.

U.S. Pat. No. 4,105,547 discloses a membrane filtration involving a recirculation of the fluid to be filtered on the retentate side of the filter membrane and a recirculation of the filtered fluid, i.e. the permeate, on the permeate side of the filter membrane. The two streams flow in the same direction, i.e. cocurrently, along the respective sides of the filter membrane so as thereby to ensure a uniform drop of pressure across the entire membrane. The object of such an assembly is to optimize the filtration capacity of the membrane. In practice the suitable equilibrium is obtained by adjusting the pressure on the permeate side. In order to obtain a sufficiently high pressure of the recirculated permeate a high pumping capacity is, however, necessary, especially in case of a high amount of permeate. Such a high requirement to the pumping capacity resulted, however, in operation costs which were considered unacceptable.
EP-PS No. 333,753 describes an improved membrane filtration assembly of the above type, where several membrane units in form of tubular membrane filters with surrounding tubular supporting structures are arranged in parallel in a common collecting space. In order to ensure a suitable, uniform drop of pressure along the permeate side, the collecting space of the membrane is filled with filler bodies. As a result a considerable, mechanical impediment to the flow of the circulating permeate is obtained. In order to retain the filler bodies in the collecting space and in order to distribute the stream of the circulating permeate, means are provided in the known assembly, at least at the inlet side, said means being provided in form of a disk with holes abutting an outer housing defining the collecting space. The disk with holes retains the filler bodies in the collecting space and distributes the stream of circulating permeate thereacross.
The use of filler bodies ensures an adjusted flow resistance to the permeate stream. The system involves, however, also some problems. The replacement of merely a single membrane unit necessitates a removal of all the filler bodies from the entire permeate collecting space. Thus the replacement of a unit is very difficult and time-consuming. In addition, the filler bodies render it difficult to clean the permeate space by way of circulation of cleaning fluid.
It turned out surprisingly that a membrane filtration assembly of the type mentioned in the introduction can be constructed in such a manner that the cleaning is facilitated and the replacement of membrane units is very easy because the use of filler bodies has been completely avoided.
The object of the present invention is to provide an alternative membrane filtration assembly where the above drawbacks of the assembly described in the EP-PS No. 333.753 are avoided while the desired uniform drop of pressure across the entire membrane surface is maintained in a very economical manner.


A robotic hand with finger assemblies to better simulate human hand form factors and gestures. For each finger assembly, the robotic hand includes a finger drive assembly that is operable to selectively apply tension to four elongated and flexible tension elements (e.g., steel cable). Each of the finger assemblies includes a set of links or link members that are actuated or moved by the selective tensioning/movement of the tension elements by the drive assembly. The links are interconnected with pivotal joints such that they have three degrees-of-freedom, and the finger assembly includes a set of pulleys that are supported on the links and that are arranged to provide support and to guide the tension elements through the finger assembly. The tension elements preferably extend only partially about any one of the pulleys, whereby the finger assembly utilizes “n+1” actuation with non-helical wrapping of the tension elements.

1. Field of the Invention
The present invention generally relates to robotics and, more particularly, to a robot hand that includes fingers designed to fit within a human form factor and to move and behave more like fingers of a human hand.
2. Relevant Background
In recent years, there has been an increasing demand for robots that more closely simulate or mimic humans. For example, animatronic figures are robotic systems that are designed to duplicate characters as closely possible, and many of these characters are human or human-like characters. Robots used to provide animatronic figures may be displayed as part of rides, attractions, theater shows, retail displays, and other entertainment venues. In these settings, there is desire for the animatronic figures or robots to mimic the character, such as a character from a movie or animated film, in terms of their shape, dexterity, and ability to produce motions and forces (e.g., dynamics of a mimicked character). In addition, it may be useful for a robot to be designed to reproduce physical abilities such as walking and manipulating objects such as with fingers of a robotic hand. Many characters are made to have human characteristics or features such as hands, fingers, and the like, even when they are not a human or human-like, e.g., ants, birds, monsters, and so on with human-like hands and fingers.
Increasingly, robot designers and manufacturers are being requested to design robotic systems with human-like or anthropomorphized features and capabilities to be used in non-entertainment applications. These uses may include a robot designed for patient care in a hospital or physical therapy setting, home care for a patient, or a robot for performing household tasks. In these applications, robotic systems are expected to interact with humans in a useful manner but also in an appealing manner. Robots are generally found more appealing when they look and behave in a manner familiar to humans, and it has generally been accepted that an effective human-robot interaction is provided by a human-like robotic system or a robot with human characteristics or features such as hands and fingers.
In entertainment and other applications, a challenging and important aspect is the design of the hands of the robot. For example, the hands of a robotic character, even if the character does not have human hands, are typically designed in an attempt to mimic the form, dexterity, dynamics, and functionality of human hands. Unfortunately, none of the existing robotic hand designs have successfully met all the design challenges in presenting a robotic human hand. There are numerous end-effector designs in existence, but these are generally variations of simplistic two-fingered grippers or jaws with a single degree-of-freedom that are used to grasp or clamp objects.
Several robotic "hands" have been produced, but some of these designs only bear a greater resemblance to human hands than the two-clawed gripper but typically are lacking in terms of dexterity and form. For example, a human finger has four degrees-of-freedom (DOF) (although only 3 DOF are typically controlled independently). However, robotic hands typically have much fewer DOF with some hands only providing one DOF per band, which significantly limits their dexterity and motion capability. Some will provide one DOF per finger such that each finger can be articulated independently. However, the finger motion may be a simplistic motion such as curling upon itself with no side-to-side motion of each finger or independent movement of parts or digits of the fingers as found in a human hand.
Existing robot hands that provide increased numbers of DOF often are very complex or fail to match a human form factor. For example, one existing hand design provides 24 DOF total for the hand with relatively good finger form factor compliance, but this hand design requires the number of cables (or "tendons") and actuators to be up to twice the number of DOF or forty-eight in this case. This results in a large form factor at the wrist and forearm that is less human in appearance. An additional problem with this hand design is that the cables or tendons used to actuate the finger movements run over fixed, un-lubricated metal or plastic runners creating significant friction and wear issues.
Another hand provides two digits for each "finger" and utilizes a pulley and actuator mechanism that does not lend itself to being packaged with human form factor (e.g., thin elongated fingers, a relatively small wrist, and thin palm). Particularly, in this hand design, an "n+1" arrangement is used for the drive cables or tendons, which reduces the number of cables required, but the pulley arrangement is such that the cables each wrap about their supporting pulleys by more than 360 degrees, which requires that the pulleys be thick (e.g., generally twice the cable thickness) making it difficult to place in a finger form factor packaging. Also, the cables create additional friction and wear as they cross over one another and rub upon each other during operation of the hand. Further, this robot hand requires four motor drives per finger, which increases costs, complexity, form factor, and maintenance.
Yet other robotic hands may be designed to use a thicker cable and actuate the fingers with a push/pull arrangement. Motors are proximally mounted to the wrist that is used to support the hand. To transmit power through the wrist, flexible drive shafts are used, with rotary motion as opposed to linear motion being transmitted through the wrist. This rotary motion is converted to linear motion by means of lead screws mounted in the palm of the hand. This provides the advantage of passing a number of drive shafts equal to the number of DOF of the hand (e.g., twelve in one example of this design). However, one disadvantage of the rotary drive hand is that twelve lead screws must be packaged within the palm of the hand, resulting in a large (i.e., greater than human-sized) palm. Also, the use of a thick cable in a push/pull arrangement to actuate the finger DOF limits the amount of force that may be applied in the "push" direction, which may limit the uses of this robotic hand design.
Hence, there remains a need for hand design for a robot or robotic system that meets the challenges associated with a human form factor while achieving the functionality expected of a human hand. It is preferable that such a hand design would include fingers with a similar number of digits as found in a human hand and with dexterity and movement that is more human like (e.g., fingers that move with a similar number of DOF). It is also preferable that the robot hand design includes a relatively small number of components and addresses wear and maintenance issues associated with use of actuating cables (or tendons).


The present invention relates to a process for the preparation of xcex3-lactams of the general formula I

This application claims priority from German Application No. 198 22 912.7, filed on May 22, 1998, the subject matter of which is hereby incorporated herein by reference.
1. Field of the Invention
The present invention relates to a process for the preparation of compounds of the general formula I and their salts
wherein
R1 may represent H, (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkynyl, (C2-C8)-alkoxyalkyl, (C1-C8)-acyl, which are optionally linear or branched and may be mono- or poly-substituted by halogens, by radicals containing N, O, P, S atoms, (C3-C7)-cycloalkyl, which may be saturated or unsaturated and mono- or poly-substituted by linear or branched (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkynyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl, by halogens, by radicals containing N, O, P, S atoms, or may contain hetero atoms such as N, O, P, S in the ring, aryl, such as phenyl or naphthyl, aralkyl, such as benzyl or phenethyl, heteroaryl, such as furyl, pyrrolyl, pyridyl, heteroaralkyl, such as furfuryl, pyrrolylmethyl, pyridylmethyl, furylethyl, pyrrolylethyl, pyridylethyl, wherein the rings just mentioned may optionally be mono- or poly-substituted by linear or branched (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkynyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl, by halogens, by radicals containing N, O, P, S atoms, N-bonded amino acid or peptide residue,
R2 may represent H, (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkynyl, (C2-C8)-alkoxyalkyl, which are optionally linear or branched and may be mono- or poly-substituted by halogens, by radicals containing N, O, P, S atoms, (C3-C7)-cycloalkyl, which may be saturated or unsaturated and mono- or poly-substituted by linear or branched (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkynyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl, by halogens, by radicals containing N, O, P, S atoms, and/or may contain hetero atoms such as N, O, P, S in the ring, aryl, such as phenyl or naphthyl, aralkyl, such as benzyl or phenethyl, heteroaryl, such as furyl, pyrrolyl, pyridyl, heteroaralkyl, such as furfuryl, pyrrolylmethyl, pyridylmethyl, furylethyl, pyrrolylethyl, pyridylethyl, wherein the rings just mentioned may optionally be mono- or poly-substituted by linear or branched (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkynyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl, by halogens, by radicals containing N, O, P, S atoms,
R3 may represent H, ClCO, (C3-C8)-acyl, which may optionally be linear or branched, a C-bonded amino acid or peptide residue or a conventional peptide-protecting group such as, for example, formyl, carbamoyl, benzyloxycarbonyl, tert.-butyloxycarbonyl, allyloxycarbonyl, trifluoroacetyl.
The invention relates also to novel intermediates of the general formulae V, IV and II and their salts
wherein R1, R2, R3 are as defined above and R4 represents (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkoxy, (C2-C8) alkenyloxy, which are optionally linear or branched and are optionally substituted by one or more halogen atoms, aryl, such as phenyl or naphthyl, aralkyl, such as benzyl or phenethyl, arylalkyloxy, such as benzyloxy, and R5 represents H, or R5 and R3 are bonded together via a Cxe2x95x90O group to form a ring, wherein in formula V, when R2 is H, R3 may not be H, and to the uses of those intermediates.
2. Background Information
The compounds that can be prepared by the process according to the invention and the novel intermediates are valuable intermediates for the production of biologically active substances. For example, 3-amino-2-oxo-pyrrolidines are preferably used as a structural unit for peptide mimetics, which are used as pharmaceuticals. In WO 94/22820, 3-amino-1-phenyl-2-oxo-pyrrolidines substituted at the phenyl ring, for example, are described as intermediates for thrombocyte aggregation inhibitors. Other biologically active compounds containing those xcex3-lactams have been studied by Kottirsch et al. (Bioorg. Med. Chem. Lett. 1993, 3, 1675). In other examples, they are used in highly potent neurokinin NK-2 receptor antagonists according to Deal et al. (J. Med. Chem. 1992, 35, 4195).
The majority of the processes used hitherto for the preparation of substituted 3-amino-2-oxo-pyrrolidines consist in first converting the corresponding open-chained methionine compounds into their sulfonium salts and cyclising the latter with strong bases in a suitable solvent. Friedinger et al. (J. Org. Chem. 1982, 47, 104-109) use for that purpose methyl iodide and sodium hydride, which is difficult to handle in a large-scale process. In U.S. Pat. No. 5,484,946, trimethylsulfonium or trimethylsulfoxonium salts are used for the alkylation instead of methyl iodide, which is readily volatile. The cyclisation is then carried out using potassium carbonate.
However, the main problem of those procedures, namely the unavoidable release from the methionine precursor of dimethyl sulfide, which is extremely strong-smelling, cannot be avoided in the process just mentioned either. Moreover, the necessary use of expensive aprotic polar solvents such as, for example, DMSO in the cyclisation with potassium carbonate appears to be a further disadvantage.
WO 94/22820 mentions a process in which racemic homoserine derivatives, which have been prepared starting from butyrolactone, are cyclised to pyrrolidones by means of triphenylphosphine and azodicarboxylic acid diesters. However, those reagents are not very suitable for use in an industrial process since they are relatively expensive. Moreover, the cyclisation in that variant yields a number of secondary products which are difficult and hence time-consuming and expensive to separate from the desired derivative (K. Nakajima et al. Peptide Chemistry 1983, 77-80).
Although L-homoserine is a naturally occurring amino acid, as yet there are known only a relatively small number of syntheses of homoserineamides, for example peptides, that start from homoserine. The reasons therefor are that homoserine and the corresponding N-acyl compounds very readily form the corresponding lactones under acid conditions (J. P. Greenstein, M. Winitz, xe2x80x9cChemistry of the Amino Acidsxe2x80x9d, Wiley, N.Y. 1961, Vol. 3, p. 2612). The same also occurs when the carboxy group is activated, as is necessary for the preparation of homoserineamides.
Although it is possible to react also N-acylhomoserine-lactones with alkylamines and amino acid esters or amino acid salts to form the corresponding amides (Sheradsky et al., J. Org. Chem. 1961, 26, 2710), the reaction requires either very long reaction times or relatively high temperatures. For that reason, this method has not been used for the preparation of complex, optionally optically active compounds.
For the preparation of homoserineamides there are used homoserine derivatives in which the hydroxy function is protected by a suitable group. Hitherto, that was achieved either by a trityl group (Barlos et al., J. Chem. Soc., Chem. Commun. 1986, 1259), by mono- or di-methoxytrityl groups (Beltran et al., Lett. Pept. Sci. 1997, 4, 147), tert.-butyldimethylsilyl group (WO 97/46248) or benzyl groups (Cornille et al., J. Am. Chem. Soc. 1995, 117, 909). The disadvantage of those protecting groups is that they either require expensive chemicals or can be introduced only in a complicated manner.
O-Acyl compounds could be simple and inexpensive protecting groups. However, the problem with those compounds is that they very rapidly undergo an O- greater than N-acyl shift under basic conditions, with formation of the corresponding N-acylhomoserines. Furthermore, for the preparation of O-acetylhomoserine there has hitherto been described only the reaction of homoserine with acyl anhydrides in perchloric acid which, on account of the explosive tendency of perchlorates, appears to be very disadvantageous and unsuitable for larger batches. The yields are only 51% at the most (Nagani et al., J. Biol.
Chem. 1967, 242, 3884).
Accordingly, the object of the present invention is to provide a further process for the preparation of xcex3-lactams of the general formula I which can advantageously be carried out on an industrial scale, that is to say which avoids the use of critical substances and expensive reagents as far as possible. Within the context of the invention, critical substances are to be understood as being compounds which, when used on a large scale, give rise to particular risks as regards environmental pollution or health and safety at work.
Another object of the present invention is to provide a process which allows the xcex3-lactams of the general formula I to be prepared without formation of the foul-smelling dimethyl sulfide.
A further object of the invention is to provide novel intermediates which can advantageously be used for the synthesis of the xcex3-lactams of the general formula I, and to indicate an advantageous use of those intermediates.
These and other objects, which are not explained in greater detail but which readily follow from the prior art in an obvious manner, are the subject of a process having the features of the characterising clause of claim 1. Advantageous developments of the process according to the invention are described in the sub-claims which are dependent on claim 1. Claims 26 to 34 achieve the object of providing novel intermediates. In claim 35 there is described an advantageous use of the intermediates.
By synthesising a compound of the general formula I and its salts
wherein
R1 may represent H, (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkynyl, (C2-C8)-alkoxyalkyl, (C1-C8)-acyl, which are optionally linear or branched and may be mono- or poly-substituted by halogens, by radicals containing N, O, P, S atoms, (C3-C7)-cycloalkyl, which may be saturated or unsaturated and mono- or poly-substituted by linear or branched (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkynyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl, by halogens, by radicals containing N, O, P, S atoms, and/or may contain hetero atoms such as N, O, P, S in the ring, aryl, such as phenyl or naphthyl, aralkyl, such as benzyl or phenethyl, heteroaryl, such as furyl, pyrrolyl, pyridyl, heteroaralkyl, such as furfuryl, pyrrolylmethyl, pyridylmethyl, furylethyl, pyrrolylethyl, pyridylethyl, wherein the rings just mentioned may optionally be mono- or poly-substituted by linear or branched (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkynyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl, by halogens, by radicals containing N, O, P, S atoms, N-bonded amino acid or peptide residue,
R2 may represent H, (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkynyl, (C2-C8)-alkoxyalkyl, which are optionally linear or branched and may be mono- or poly-substituted by halogens, by radicals containing N, O, P, S atoms, (C3-C7)-cycloalkyl, which may be saturated or unsaturated and mono- or poly-substituted by linear or branched (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkynyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl, by halogens, by radicals containing N, O, P, S atoms, and/or may contain hetero atoms such as N, O, P, S in the ring, aryl, such as phenyl or naphthyl, aralkyl, such as benzyl or phenethyl, heteroaryl, such as furyl, pyrrolyl, pyridyl, heteroaralkyl, such as furfuryl, pyrrolylmethyl, pyridylmethyl, furylethyl, pyrrolylethyl, pyridylethyl, wherein the rings just mentioned may optionally be mono- or poly-substituted by linear or branched (C1-C8)-alkyl, (C2-C8)-alkenyl, (C2-C8)-alkynyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl, by halogens, by radicals containing N, O, P, S atoms,
R3 may represent H, ClCO, (C1-C8)-acyl, which may optionally be linear or branched, a C-bonded amino acid or peptide residue or a conventional peptide-protecting group such as, for example, formyl, carbamoyl, benzyloxycarbonyl, tert.-butyloxycarbonyl, allyloxycarbonyl, trifluoroacetyl, by cyclising derivatives of the general formula II
wherein R1, R2, R3 are as defined above and X represents an element from the group halogen, sulfonic acid ester, the desired compounds of the general formula I are obtained in good yields in a very simple and nevertheless advantageous manner, the process according to the invention being predestined for a large-scale industrial process owing to the fact that the starting materials necessary for the synthesis are relatively inexpensive, the reaction is simple to perform, the yields are good, and dangerous or foul-smelling reagents are not used.
Within the context of the process according. to the invention, a sulfonic acid radical X is to be understood as being any radical derived from a sulfonic acid of the structure HOSO3Rxe2x80x2, wherein Rxe2x80x2 in this connection represents a linear or branched (C1-C8)-alkyl radical or an aryl radical which may optionally be substituted by one or more (C1-C8)-alkyl radicals. The mentioned radicals may optionally be substituted by one or more elements from the group halogen, preferably Cl or F.
The above-described cyclisation may advantageously be carried out under basic conditions, it being possible to use as the base preferably an alkali hydroxide. The use of aqueous alkali hydroxide solution is especially preferred, and very special preference is given to the use of sodium hydroxide solution for the cyclisation. Compounds of the general formula II that can advantageously be used for the cyclisation possess a sulfonic acid ester as the leaving group X, and the use of the so-called mesyl (OSO3Me) group is especially preferred.
This process can be applied very especially to compounds of the general formula II wherein R1 is a p-cyanophenyl or p-carbamoylphenyl radical, while R2 is advantageously H and R3=benzyloxycarbonyl.
The cyclisation can be carried out at temperatures of from xe2x88x9220xc2x0 C. to 100xc2x0 C. Temperatures of from 0xc2x0 C. to 50xc2x0 C. are preferably employed in the cyclisation, very especially temperatures of from 10xc2x0 C. to 30xc2x0 C.
The synthesis of the compounds of the general formula I can preferably and extremely simply be accomplished from compounds of the general formula II, if II is reacted to form I without being isolated beforehand.
The compounds of the general formula II can advantageously be prepared from derivatives of the general formula III
wherein R1, R2, R3 are as defined above. The compounds of the general formula III are preferably not isolated before being processed further to form compounds of formula II.
The compounds of formula III, in turn, are very especially preferably prepared from compounds of the general formula IV
wherein R1, R2, R3 are as defined above and R4 represents (C1-C8)-alkyl, (C2-C8)-alkenyl, (C1-C8)-alkoxy, (C2-C8)-alkenyloxy, which are optionally linear or branched and are optionally substituted by one or more halogen atoms, aryl, such as phenyl or naphthyl, aralkyl, such as benzyl or phenethyl, arylalkyloxy, such as benzyloxy.
In principle, any processes for hydrolysis known to the person skilled in the art can be used for the above-mentioned conversion. Advantageously, however, compounds of the general formula IV can be converted into compounds of the general formula III by aminolysis. Special preference is given in this connection to the use of ammonia as the amine; very especially preferably, ammonia can be employed in the form of its aqueous solution.
The compound of the general formula IV, in turn, can advantageously be prepared from compounds of the general formula V
wherein R2, R31, R4 are as defined above and R5 represents H, or wherein R3 and R5 are bonded together via a Cxe2x95x90O group to form a ring. Before they are reacted to form compounds of the general formula IV, compounds of the general formula V wherein R5 is H can be activated preferably by means of acid chlorides (analogously to Houben-Weyl, Volume 15, Part 2, p. 169 ff). Compounds of the general formula V wherein R3 and R5 are bonded together via a Cxe2x95x90O group to form a ring can advantageously be converted into compounds of the general formula IV wherein R3 represents H.
According to the invention, the compounds of the general formula V can advantageously be prepared from the acid addition salts of the general formula VI
wherein R2, R4 are as defined above and Y"THgr" is the corresponding base of an inorganic acid, by reaction with an acylating reagent derived from R3. Within the scope of the invention, an inorganic acid is to be understood as being an acid whose pKa value is less than 2.5, such as, for example, HCl, HBr, H2SO4, H3PO4. Phosgene can preferably be used as the acylating reagent. In that case, compounds of the general formula V wherein R3 and R5 are bonded together via a Cxe2x95x90O group to form a ring are obtained. Alternatively, compounds of the general formula VI can be obtained by reaction with acylating reagents from the group of the organic anhydrides, such as, for example, di-tert.-butyl pyrocarbonate, of the activated esters, such as, for example, trifluoroacetic acid ester, acetic acid hydroxysuccinimide ester, or of the halocarbonic esters, such as, for example, benzyloxycarbonyl chloride, allyloxycarbonyl chloride or tert.-butyloxycarbonyl fluoride. The above-described acylation can preferably take place in aqueous solution at a pH of from 4 to 9; it is especially preferred to maintain a pH range of from 6.5 to 7.5 in that reaction. The acylation to form compounds of the general formula V wherein R5 is H can, however, also be carried out in organic solvents in the presence of a tertiary base. Triethylamine may advantageously be used as the tertiary base.
The acid addition salt of the general formula VI, in turn, can preferably be prepared from compounds of the general formula VII
wherein R2 is as defined above. The reaction can take place in a mixture of a carboxylic acid R4COOH and the carboxylic acid chloride or bromide R4COCl or R4COBr, respectively, wherein R4 is as defined above. For that reaction it is advantageous first to mix together the appropriate carboxylic acid R4COOH and the corresponding carboxylic acid halide R4COHal and then to add the compound of the general formula VII to that mixture. The above-mentioned process is advantageously carried out at a temperature of from xe2x88x9220xc2x0 C. to 50xc2x0 C., preferably from xe2x88x9210xc2x0 C. to 20xc2x0 C. and especially from xe2x88x925xc2x0 C. to 10xc2x0 C.
Another preferred variant for preparing the compound of the general formula V consists in reacting compounds of the general formula VIII
wherein the radicals R2, R3 may be as defined above and R5 represents H, with the reagent R4COZ, wherein R4 is as defined above and Z represents an activating radical. The activating radical Z may in principle be any radical known to the person skilled in the art for that purpose, such as, for example, hydroxysuccinimide, hydroxybenzotriazole, R4CO2, halogen (The Chemical Synthesis of Peptides, J. Jones, Oxford Press 1991, p. 42 ff). For the acylation of the OH function of formula VIII there are preferably used compounds in which the activating radical Z corresponds to a halogen. In that case, the reaction is very especially preferably carried out in the carboxylic acid corresponding to the carboxylic acid halide as solvent. Especially preferred halides are the chlorides or bromides of the carboxylic acid. Very special preference is given to the embodiment in which the inorganic acid formed in the acylation is buffered by addition of the sodium-salt of the corresponding carboxylic acid used as solvent.
In a further aspect of the present invention, advantageous novel intermediates of the general formulae V, IV and II and their salts are provided
wherein R1, R2, R3, R4, R5 are as defined above, wherein in formula V, when R2 is H, R3 may not be H. Preference is given to compounds in which R2 is hydrogen, R3 is a benzyloxycarbonyl, tert.-butyloxycarbonyl or tri-fluoroacetyl radical, R4 is a methyl radical and R5 is hydrogen, or in which R3 and R5 are bonded together via a Cxe2x95x90O group to form a ring. X is preferably a halogen or a sulfonic acid ester, very especially preferably an OSO3Me group. R1 is very especially preferably p-cyanophenyl or p-carbamoylphenyl.
The advantageous compounds of the general formulae V, IV and II are used according to the invention for the preparation of intermediates of biologically active substances.
The present invention is explained again in the scheme below:
The cyclisation of II to I is an intramolecular nucleophilic substitution. In principle, any variant known to the person skilled in the art may be employed for that reaction. However, a number of subsidiary products, such as, for example, the removal or substitution of the leaving group, are to be expected in that reaction. For that reason it was very surprising that it was possible to find for the cyclisation, with the choice of leaving groups X, conditions that permit the use of a relatively strong basexe2x80x94in this case sodium hydroxidexe2x80x94in the presence of a polar protic, cation-stabilising solventxe2x80x94in this case waterxe2x80x94and nevertheless allow the reaction to proceed as selectively as possible. Those very inexpensive, uncritical reagents, which can readily be used for a large-scale process, are clearly to be preferred over other conditions from the prior art for the intramolecular substitution (dimethyl sulfide is not formed, sodium hydride is not used, no expensive reagents and solvents are required). A further advantage of those preferred reaction conditions is that the optical activity of enantiomerically enriched starting compounds is maintained virtually completely under the conditions according to the invention.
In the above-described reaction there are preferably used derivatives of II that contain the p-cyanophenyl or p-carbamoylphenyl group as the radical R1, H as R2, and a benzyloxycarbonyl radical as R3. They yield advantageous compounds for the preparation of pharmaceuticals, as described, for example, in WO 94/22820.
The preparation of the compounds of formula II from III can be carried out analogously to processes known from the literature. It is, however, preferred to form a sulfonic acid ester from III and sulfonic acid chloride, which ester can advantageously be reacted further in the manner indicated above, without being isolated as an intermediate, to form I. Special preference is given to the use of the mesyl (OSO3Me) group, which can be introduced using mesyl chloride and triethylamine as base. It is astonishing that under the preferred reaction conditions according to the invention it is not the hydrolysis of the sulfonic acid ester II but the cyclisation that is the main reaction. That was not foreseeable. It is also especially advantageous that the compounds of the general formula II do not have to be isolated before they are reacted to form I. They are formed and then preferably reacted in situ.
The preparation of the compounds of the general formula III from the compounds of the general formula IV can be carried out by acid or basic hydrolysis of the O-acyl group. Under those conditions, however, partial hydrolysis, for example of the N-acyl group which may be present and of the amide bond, may occur. Under the preferred hydrolysis variant, therefore, the removal of the O-acyl group is carried out by aminolysis. Ammonia is especially preferably used for that purpose, very especially preferably its aqueous solution. Under those conditions, the O-acyl group is removed selectively.
According to the invention it is also not necessary to isolate the compounds of the general formula III. They can also be reacted directly to form compounds of the general formula II. For the present process it is, therefore, extremely advantageous to select a process variant in which, starting from derivatives of the general formula IV to the end product of the general formula I, no intermediate stage is isolated intermediately. Nevertheless, the derivatives of the general formula I are obtained in good to very good yields and with a very high degree of purity. That was surprising and could in no way be foreseen; it is, however, all the more advantageous for a large-scale process since the very cost-intensive handling of isolated intermediate products can be reduced to a minimum.
There may be used as solvents for the conversion of IIIxe2x86x92II any organic solvents that are inert under the given conditions. Special preference is given to ethers, such as, for example, methyl tert.-butyl ether, tetrahydrofuran, dimethoxyethane, dioxane, hydrocarbons, such as, for example, hexane, cyclohexane, toluene, ketones, such as,. for example, acetone, diethyl ketone, methyl isobutyl ketone, and carboxylic acid alkyl esters, such as, for example, ethyl acetate, isopropyl acetate, n-butyl acetate. Very special preference is given to organic solvents that form a low-boiling azeotrope with water, such as, for example, toluene, methyl isobutyl ketone or n-butyl acetate.
Compounds of formula IV, in turn, can preferably be obtained from derivatives V. In the case where-the radicals R3 and R5 are bonded together via a Cxe2x95x90O group to form a ring, that is to say an N-carboxylic acid anhydride of the derivative in question is present, the carboxy function of the homoserine derivative does not have to be activated for the coupling. The derivatives are then simply reacted with the chosen amine, yielding compounds of formula IV wherein R3 is H. The latter can be converted into the corresponding N-acyl compounds in accordance with processes known from the literature by reaction with an acylating reagent derived from R3.
In the case where R5=H, the carboxy function is activated before coupling with the amine. That is effected by methods of peptide chemistry known to the person skilled in the art (Houben-Weyl, Volume 15, 2nd part), such as, for example, via mixed anhydrides, activated esters, etc. Reaction with an acid chloride, such as, for example, pivaloyl chloride, to form the mixed anhydride is, however, preferred.
The compounds of the general formula V according to the invention can be obtained from homoserine derivatives such as VII by two different methods. Either VII is first acylated at the oxygen to form VI and then processed further at the nitrogen by N-acylation to form V, or compounds of the general formula VIII, which are obtainable from VII by N-acylation, are converted into V by O-acylation.
The N-acylation to form the homoserine derivative VIII can be carried out analogously to that of other amino acids (Houben-Weyl, Volume 15, Part 1 and Part 2). In principle there may be used as the acylating reagents any acylating reagents derived from R3, such as amino-protecting reagents, C-terminal activated amino acids or peptides.
In the isolation of the N-acylhomoserines of formula VIII there was, however, the problem that those compounds, as the free acid, are very unstable and readily cyclise to form the corresponding lactones. That cyclisation is catalysed by acids and, moreover, always occurs when the acid function is activated. It takes place also in the reaction with the activated acid derivative R4COZ under the basic conditions which are otherwise customary for acylations. However, if the O-acylation is carried out in, as solvent, the carboxylic acid R4COOH corresponding to the reagent R4COZ used for the O-acylation, then the desired derivatives V are obtained almost exclusively. Special preference is given to the use of Cl for Z. A base is optionally and advantageously used to buffer the acid that forms during the reaction. The sodium salt of the carboxylic acid used as solvent is advantageously added as the base. The subsidiary product, the lactone, which is also formed in that process but to a lesser extent can be separated from the product mixture in a simple manner by extraction and, after ring-opening, is available for the reaction again.
In the second variant, the O-acylation to form derivatives VI is carried out according to the invention in a medium that helps to prevent the N-acylation, since that would be the more rapid reaction. The reaction is, therefore, preferably carries out in a carboxylic acid such as R4COOH, to which the appropriate corresponding carboxylic acid halide, preferably carboxylic acid chloride, has previously been added. When the homoserine derivative VII is subsequently added, protection of the amino function of VII takes place by protonation as a result of the strong inorganic acid that forms in the solvent, and acylation of the hydroxy function preferentially occurs. The acid addition salt of the hydroxy-protected homoserine VI is therefore obtained as the product. The use of the dangerous perchloric acid, as is known from the prior art, is thus avoided. Furthermore, the yields in the process according to the invention are markedly better.
The further reaction of derivatives VI to form V can in principle be carried out by processes known to the person skilled in the art using an acylating reagent derived from R3, such as amino-protecting reagents, C-terminal activated amino acids, peptides, or using phosgene. There was the problem, however, that the O-acylhomoserines VI rapidly undergo an Oxe2x86x92N-acyl shift under basic conditions. According to the process of the invention, that can be avoided by maintaining the pH range, if the acylation is carried out in an aqueous medium, at from 3 to 9, preferably from 6 to 7.5. A further possibility is to react the O-acyl compounds VI in anhydrous solvents and triethylamine as base. For the reaction with phosgene, the acid addition salt VI can be used without addition of a base.
There come into consideration as linear or branched (C1-C8)-alkyl radicals methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl or octyl, including all possible isomers of constitution. The linear or branched (C2-C8)-alkenyl radical includes all the substituents.listed above in connection with the (C1-C8)-alkyl radical with the exception of the methyl radical, at least one double bond being present in those radicals. The scope of (C2-C8)-alkynyl corresponds to that of (C2-C8)-alkenyl, but at least one triple bond must be present in that case. The radical (C1-C8)-alkoxy corresponds to the radical (C1-C8)-alkyl, with the proviso that it is bonded to the ring via an oxygen atom. (C2-C8)-Alkoxyalkyl radicals are radicals in which the alkyl chain is interrupted by at least one oxygen function, wherein two oxygens may not be bonded together. The number of carbon atoms indicates the total number of carbon atoms contained in the radical. (C2-C8)-Alkenyloxy is to be understood as meaning radicals such as (C2-C8)-alkoxy that have at least one C-C double bond. Radicals containing N, O, P, S atoms are especially alkyl, alkenyl, alkynyl radicals of the above-mentioned type that have one or more of those hetero atoms in their chain or that are bonded to the molecule via one of those hetero atoms. (C3-C7)-Cycloalkyl is to be understood as being cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl radicals.
There are suitable as halogens fluorine, chlorine, bromine and iodine.
An N-bonded amino acid or peptide residue is to be understood as being a compound in which the molecule in question is bonded via its N atom to the xcex1-carbon atom of a carboxylic acid derived from an amino acid, which carboxylic acid may be part of a peptide residue.
A C-bonded amino acid or peptide residue is to be understood as being a compound in which the molecule in question is bonded via its N atom to the carbon atom of the carboxyl group of an amino acid, which may be part of a peptide.
(C1-C8)-Acyl is to be understood as being an alkyl radical having from one to eight carbon atoms, which may be linear or branched, that is to say which likewise includes all the possible isomers of constitution, and which is bonded to the molecule via a Cxe2x95x90O function.
Within the scope of the invention, compounds having a stereogenic centre mean racemates as well as the enantiomeric antipodes of those structures. However, for the process according to the invention it is preferred to use enantiomerically enriched homoserine derivatives of the general formula VII. Thus, when the enantiomerically enriched starting materials (D or L) are used, the ID enantiomerically enriched products of the general formulae V and I (D or L) are obtained with virtually complete stereoconservation.
Salts are to be understood as being ionic addition compounds from strong acids such as HCl , HBr, H2SO4, H3PO4, CF3COOH, p-toluenesulfonic acid, methanesulfonic acid and the molecule in question.

Process for the preparation of 3-amino-2-oxo-pyrrolidines, novel intermediates and their use

Abstract: The invention relates also to novel advantageous intermediates of the general formulae V, IV and II and their salts

Abstract: and their use.

Abstract: The compounds of the general formula I are obtained by cyclising compounds of the general formula II

Abstract: which can be prepared from the intermediate compounds V.


A casing of a solid-propellant engine comprising a core and a layer of elastomeric material, set as coating for at least part of the core to provide a thermal protection of the core itself is obtained by: inserting the core in a forming mould so as to make within the mould two annular chambers separated from one another by the core; forming a strand of elastomeric material; obtaining a defined portion of elastomeric material by cutting the strand transversely to size in an external environment; and injecting the cut portion of elastomeric material simultaneously within both of the annular chambers.

As is known, a solid-propellant engine comprises a casing filled with solid propellant, a device for ignition of the propellant, and a terminal nozzle, through which the propellant, by burning, generates a desired propulsive thrust. The casing comprises a core made of steel or of a composite material, which has a cylindrical tubular portion and a closing portion shaped like a spherical cap and is insulated by being coated both internally and externally with a layer of specific thermally insulating material to define an adequate thermal protection of the core.
Normally, the layer of thermally resistant material is obtained by forming separately from the core two shells or caps, which, once the core has been formed in vacuum conditions, are, one, inserted within the core bringing it into contact with the internal surface of the core itself and, the other, fitted on the core causing it to adhere to its outer surface. Once the coupling is terminated, the caps are vulcanized in autoclave to complete the coating.
The known modality of insulation just described requires three dedicated apparatuses that are different from one another, two for making the caps and the third for assembling the caps themselves on the core. For these reasons, the mode of insulation described involves extremely long times and high costs of implementation, there being necessary three distinct working steps, rendered, on the other hand, even more complex by the particular geometry of the casing. However accurate the operations of production of the shells or caps may be, these frequently have defects and dimensional instability, randomly distributed porosities, and for this reason induce positioning errors or faults.
Even though the maximum care is then taken in positioning and in the subsequent operation of vulcanizing, between the caps and the core there are frequently present areas in which they are not properly stuck together, which, along with the aforesaid porosities, jeopardize sensibly the efficiency of the insulation and consequently the reliability of the casing.

Method and plant for the production of a casing for a solid-propellant engine