A multileveled bonus round having a plurality of random generations, differing average awards and differing levels of risk. The gaming device contains a display that prompts the player to select one of a plurality of pick buttons. When the player does so, the game assigns an award set to each pick button of the display. The game then displays each of the awards in the award sets so that the player can easily recognize the assignments. The game randomly chooses one of the awards from each of the award sets and displays the chosen awards. The player's award for any given level is thus the selected award of the selected award set of the picked or chosen pick button. The awards of the present invention can be an award multiplier, outright base game credits or a bonus round terminator. A bonus round terminator terminates the bonus round. The game proceeds though all the levels of the round in the manner just described until the game selects a bonus round terminator or the player exhausts all the levels.

Gaming machines currently exist with bonus rounds in which a player has one or more opportunities to choose masked bonus awards from a group of symbols arranged in a pattern and displayed to the player. When the player chooses a masked symbol from the pattern, the bonus round removes the mask and either displays a bonus value or a bonus round terminator which terminates the bonus round. The controller of the gaming machine randomly places a predetermined number of bonus round awards and bonus terminators in the pattern at the beginning of the bonus round and maintains the positioning until the bonus round terminates. The outcome depends upon whether the player selects an award or terminator.
European Patent Application No. EP 0 945 837 A2 which is assigned on its face to WMS Gaming, Inc. discloses a bonus round of this type. In this type of round, each time the player enters the bonus round, the player has the same diminishing chance to select an award instead of a terminator. For example, that application discloses a bonus round that has 30 possible selections, 24 bonus awards and 6 bonus round terminators. Each time the player enters the bonus round, the player has a 100% chance of having a first pick, an 80% chance of having a second pick, a 63% chance of having a third pick, a 50% chance of having a fourth pick and so on.
It should be appreciated that once a bonus round of the type described above begins, the game will not change or alter the values of the masked awards. Once the game displays the masked awards, the game sets the values and positions for each award and does not alter either during the round. Therefore, the implementor of the above type of bonus round has one opportunity to generate or distribute awards having relatively high and low values.
For example, the application discloses a bonus round that has one 20 credit award, two 15 credit awards, two 10 credit awards, eight 5 credit awards, two 4 credit awards, three 3 credit awards, four 2 credit awards and two 1 credit awards. As the player advances through this type of bonus round, the probability of the player receiving an award having a particular value, e.g., an award having a high value, only increases slightly due to the lessening of remaining selections. Likewise, as discussed above, the probability of the player obtaining a bonus terminator increases by the lessening of remaining selections.
Because the above bonus scheme has only one opportunity to generate a set of values and because the probability of selecting a particular award or a bonus terminator only increases due to the lessening of remaining selections, bonus rounds of this type have no effective ability to alter their return/risk ratio so that players will receive higher bonuses as they advance farther and farther through the bonus round. For example, in the distribution stated above, the player has a 1 in 30 or 3.33% chance of selecting the 20 credit award in the player's first selection, a 1 in 29 or 3.45% chance in the second selection, a 3.57% chance in the third selection and a 3.70% chance in the fourth selection. The player has roughly the same probability in each selection to choose the high value award.
Increasing the number of high value awards does not solve the problem. If the above example included five 20 credit awards instead of just one, the probability distribution would change to 16.7% (5 in 30), 17.2% (5 in 29), 17.9% (5 in 28) and 18.5% (5 in 27), respectively. It should be appreciated that decreasing the total number of selections has roughly the same effect as increasing the number of high value awards. Thus, in the above type of gaming device, the player has roughly the same chance of choosing a high value award in the first pick as in the second, roughly double the chance of choosing a high value award in the first two selections as in the third selection, roughly three times the chance of choosing a high value award in the first three selections as in the fourth selection and so on.
Likewise, the above type of gaming device has no effective way to increase risk from one selection to the next. There is a 6 in 30 or 20% chance of terminating the round on the first selection, a 20.7% chance of terminating on the second selection, a 21.4% of terminating on the third, a 22.2% of terminating on the fourth and so on. The above type of gaming device cannot effectively alter return, risk or return/risk.
It should be appreciated that varying award returns and risk of bonus round termination increases player excitement and enjoyment. Players enjoy playing for high bonus awards or high return rounds. Gaming devices preferably present a risk of termination that is commensurate with the likelihood or rewarding a high return, and players enjoy playing high risk, high return games. Players also enjoy playing a game that lasts an extended period of time and provides a plurality of awards. Thus, it is desirable to have a bonus round of a gaming device that provides initial selections that are relatively low return/low risk and later selections having increasingly higher returns and higher risk.

Gaming device having a bonus round with multiple random award generation and multiple return/risk scenarios


A system for directing the ionized gases which can exit from the vent openings of the arc chambers in high power circuit breakers away from the line terminals of the circuit breaker and isolating these terminals from infiltration by such gases. The system includes a deflection plate, interphase barriers and end plates mounted in proximity to the vent openings and around the line terminals.

The present invention relates to high power electrical circuit breakers and more particularly to systems for preventing direct electrical conduction and uncontrolled arcing between the line connection terminals of such circuit breakers or between these line connection terminals and electrical ground.
High power circuit breakers generally include arc chambers located inside the circuit breakers in which controlled arcing frequently occurs as electrical connectivity is broken between the contact members of the circuit breaker. Especially under short circuit fault conditions this arcing produces large amounts of hot ionized gases within the arc chambers which exit from these chambers through vent openings in the top of the circuit breaker. Unfortunately, if these ionized gases collect in the vicinity of the line terminals of the circuit breaker they may establish a conduction path between terminals connected to different phases of the line current or between the terminals and electrical ground. This can lead to massive electrical faults on the line sides of the circuit breakers and can result in the destruction of the equipment. This can be a troublesome problem with conventional high power circuit breakers which position the vent openings to the arc chambers within the circuit breaker along the top of the circuit breaker in proximity to the line terminals.
It is therefore an object of the present invention to provide a system for a high power circuit breaker which can direct ionized gases which escape from the vent openings in the circuit breaker away from the line terminals and prevent such gases from collecting in the vicinity of the line terminals.
It is another object of the present invention to provide a deflection system for deflecting hot ionized gases exiting the vent openings to the arc chambers of a high power circuit breaker forward of the circuit breaker and away from the line terminals and electrical ground.
It is a further object of the present invention to isolate the spaces in proximity to the line terminals of a high power circuit breaker from each other and from areas adjacent to the top of the circuit breaker so that ionized gases cannot infiltrate into those spaces and establish conduction paths between the different line terminals.
It is yet another object of the present invention to provide a system for deflecting the ionized gases which may escape from the vent openings of a high power circuit breaker away from its line terminals and electric ground which is inexpensive and may be conveniently installed in conjunction with the mounting of the circuit breaker within a conventional control center.

Gas deflection and isolation system for use with a high power circuit breaker


An auger shaped, fluid medium engaging member is disclosed which includes a helically or auger shaped outer region disposed about a longitudinal axis which passes through a central region of the member. The auger shaped outer region establishes at least one auger or helically shaped fluid medium engaging surface, which intercepts the flow of a fluid medium such as air or water, for effecting rotational movement of the fluid medium engaging member about its longitudinal axis. The auger shaped, fluid medium engaging member may be coupled to an electrical generator, for generating electrical energy upon rotational movement.

Although fossil fuels are in ample supply as a resource and although oil technology exists for sea floor drilling to a depth of two miles, extracting and transporting fossil fuels is akin to playing russian roulette. For example, strip mining, deep shaft mining, acid rain and oil spills all scar and pollute the earth's surface. Accordingly, more and more people are realizing that dependance upon fossil fuels for generating electricity should be minimized and ideally reduced.
As fossil fuels become more scarce, expensive and unavailable for a variety of reasons, more and more people are realizing that dependance upon fossil fuels for generation of electricity should be minimized and ideally reduced.
Apart from nuclear generated electricity, much interest exists in generating electricity utilizing renewable resources, such as wind and water power. Most traditional attempts at harnessing the wind to generate electricity include the use of windmills. Although traditional windmills have proved somewhat satisfactory, their use is limited to areas in which a reasonable amount of wind blows, such as mountain tops and western plains. These areas are often remote from civilization to accommodate the size of the windmills and their supporting superstructures. Additionally, windmills are typically noisy and aesthetically unappealing.
There are, however, many instances and locations in which particularly air flow and also water flow, could be harnessed to generate electricity if the proper generating apparatus were available. For example, airplanes in flight, moving trains, cars, trucks and buses all generate wind flow passed their structures. In addition, a considerable amount of wind is generally always present on and about high rise buildings. In all these cases, if a low profile, horizontally disposed wind generating apparatus could be provided, a substantial amount of electrical energy could be generated, enough perhaps to make the attached object more energy self sufficient.
In conjunction with wind and solar power which will definitely contribute to an ever increasing lessened dependency on fossil fuels, it is hoped that hydrogen fusion and perhaps even cold fusion will serve as alternative sources of energy. The use of these alternative sources of energy will be a many fold benefit to the planet.
Accordingly, what is needed is an auger shaped, fluid medium engaging member for an electrical generator apparatus which can generate sufficient quantities of electricity and which can be housed in a reasonably compact enclosure, to enable the apparatus to be mounted in mobile installations, such as airplanes, trains, trucks, buses and cars, masts and upper super structures of power or sail vessels, as well as in more compact areas in which a traditional windmill won't fit, such as between floors or on top of roofs of a high rise building.

Auger shaped fluid medium engaging member


Methods are provided for reducing port to port crosstalk on a multiport assembly. Steps of the method include placing at least one BEMI in at least one compensation region, disposed on a PCB. The BEMI reduces port to port crosstalk noise by generating an opposite polarity signal to an unwanted noise signal generated through port to port adjacency. The PCB includes a plurality of ports, at least including adjacent first and second ports, each of which is an RJ45 jack port. Each port of the plurality of ports includes a plurality of modular insert pins, and is associated with an IDC pin group. The at least one compensation region includes one or more regions for generating noise compensation with respect to crosstalk noise resulting from coupling between respective modular insert pins of, or IDC pins associated with, the first and second ports, respectfully.

1. Technical Field
The present disclosure relates to systems and methods that compensate for port to port crosstalk noise generated from electrical component proximity within a multiport assembly.
2. Background Art
Unshielded Twisted Pair (UTP) cable is a popular and widely used source of data transfer media because it is a very flexible and low cost media that can be used for either voice or data communications. In fact, UTP cable has rapidly become the de facto standard for Local Area Networks (LANs), in-building voice, and data communications applications. As UTP cabling continues to be an essential choice of media transmission, new and improved methods must be employed to meet the requirements of a transmitting data source. In an UTP, a pair of copper wires generally forms a twisted pair. For example, a pair of copper wires with diameters of 0.4-0.8 mm may be twisted together and wrapped with an insulated coating to form an UTP. The twisting of the wires increases the noise immunity and reduces the bit error rate (BER) of the data transmission to some degree. In addition, using two wires, rather than one, to carry each signal permits differential signaling to be utilized. Differential signaling is generally immune to the effects of external electrical noise.
The wide acceptance of UTP for data and voice transmission is primarily due to the large installed base, low cost, and ease of new installation. Demands have increased on networks using UTP systems, such as 1000 Mbit/s and 10,000 Mbit/s transmission rates, which has forced the development of industry standards requiring higher system bandwidth performance and lower noise-connecting hardware. What began as a need for connecting hardware to provide near-end crosstalk (NEXT) loss of less than −36 dB at 16 MHz, has evolved to −54 dB at 100 MHz and −34 dB at 500 MHz for category 6 and future category 6a systems, respectively. As the transmission rates have increased, so has system noise, in particular NEXT, Far-End Crosstalk (FEXT) and Alien Near-End and Far-End Crosstalk (ANEXT/AFEXT).
For any data transmission event, a received signal will consist of a transmission signal modified by various distortions. The distortions are added by the transmission system, along with additional unwanted signals inserted somewhere between transmission and reception. The unwanted signals are referred to as noise. Noise is a major limiting factor in the performance of today's communication systems. Problems that arise from noise include but are not limited to data errors, system malfunctions, and loss of desired signals.
Generally, crosstalk noise occurs when a signal from one source is coupled to another line. Crosstalk noise is also classified as electromagnetic interference (EMI). EMI occurs through the radiation of electromagnetic energy. Electromagnetic energy waves can be derived using Maxwell's wave equations. These equations are defined using two components: electric and magnetic fields. In unbounded free space, a sinusoidal disturbance propagates as a transverse electromagnetic wave. This means that the electric field vectors are perpendicular to the magnetic field vectors that lie in a plane perpendicular to the direction of the wave. NEXT noise is the effect of near-field capacitive (electrostatic) and inductive (magnetic) coupling between source and victim electrical transmissions. NEXT increases the additive noise at the receiver and therefore degrades the signal-to-noise ratio (SNR).
Crosstalk using a plug that mates to a modular insert setup such as that illustrated in FIG. 1 will increase as system speeds or system transmission frequencies increase. The transposition or twisting of the transmitting wire pair helps minimize crosstalk generated in a cable. However, coupling occurs as the signal travels through untwisted sections, such as plugs and plug contacts.
In a differential balance two wire per pair transmission system, signals that travel along each wire (or other media) are equal in amplitude but opposite in phase. These signals at any instantaneous moment in time couple electric and/or magnetic fields to adjacent lines, which reduces their SNR. The acceptable SNR depends on the type or quality of service that is required by the system. To remove the noise components, a forward signal equal but opposite to the original signal may be induced. According to Fourier's wave theory and Maxwell's theory of electromagnetic fields, by coupling the opposite phase of the transmitted signal to a previously coupled adjacent line signal, the two signals cancel each other completely and therefore remove the noise from the adjacent line.
The American National Standards Institute/Telecommunication Industry Association/Electronics Industries Alliance (ANSI/TIA/EIA) has finalized a standard defining electrical performance for systems that utilize the 1-250 MHz frequency bandwidth range for category 6 electrical performances. The increasing demand for more bandwidth and improved communication systems (e.g., Ethernet 1000BASE-T) on UTP cabling will require improved connecting hardware. The ANSI/TIA/EIA is also working on higher standards defining electrical performance for systems that utilize the 1-500 MHz frequency bandwidth range for 100 meters of UTP cabling transmission called 100 Ohm Augmented Category 6 Cabling. The TIA/EIA 568B.2-10 titled, "Transmission Performance Specification for 4 Pair 100 Ohm Augmented Category 6 Cabling" for channel link defines the specified frequency bandwidth of 1-500 MHz, and a minimum NEXT value of −33.1 dB at 100 MHz and −26 dB at 500 MHz. By increasing the bandwidth from 1-250 MHz (category 6) to 1-500 MHz (Augmented category 6, C6a), tighter controls of component noise susceptibility are necessary. With the development of new standards, new connecting hardware noise levels will have to be lower than that of old connecting hardware used in category 5e and 6 media systems. FCC part 68.500 provides standard mechanical dimensions to ensure compatibility and matability between modular plug housings of different manufacturers.
Attempts to reduce internal crosstalk noise in electrical connectors have been made. For example, U.S. Pat. No. 5,618,185 to Aekins discloses a reduced crosstalk electrical connector including a housing that receives four pairs of elongated contacts for receiving electrical signals and a printed circuit board (PCB). The PCB utilizes a single stage or cancellator section (signal compensation) for reducing NEXT. That stage contains a cancellator that is opposite the original noise magnitude's polarity. NEXT noises are reduced internally, but external noise signals relative to adjacent ports are not reduced.
Additional attempts to reduce internal crosstalk noise in electrical connectors include, for example, U.S. Pat. No. 5,997,358 to Adriaenssens et al., which discloses a reduced crosstalk electrical connector that utilizes two stages of signal compensation for reducing NEXT. The first stage is opposite the original noise polarity and the second stage is of the same polarity as the original noise.
Thus, methods for providing positive compensation to reduce crosstalk noise in connecting hardware are addressed in U.S. Pat. No. 5,618,185 to Aekins and U.S. Pat. No. 5,299,956 to Brownell et al., the contents of which are hereby incorporated by reference. Methods for providing positive and negative compensation to reduce crosstalk noise in connecting hardware is addressed in U.S. Pat. No. 6,840,816 to Aekins and U.S. Pat. No. 5,997,358 to Adriaenssens et al., the contents of which are hereby incorporated by reference.
Although previously disclosed circuitry systems described above have been used to improve and/or compensate for internal crosstalk noise, they do not improve external crosstalk noise, such as ANEXT or AFEXT. ANEXT is the coupled crosstalk noise that occurs from one adjacent signaling media port to another signaling media port at the near-end of transmission. AFEXT is the coupled crosstalk noise that occurs from one adjacent signaling media port to another signaling media port at the far-end (received) transmission. The prior art strictly deals with internal noise issues of a connecting hardware and does not reduce external noise generated by other signal path components.
A need exists for an improved UTP connector that reduces internal as well as external noise, generated by adjacent ports, for all frequencies, e.g., up to and including the category 6a transmission levels. Moreover, a need exists for systems/techniques for rebalancing of noise on a single controlled source that contains non-interchangeable components. A further need exists for an improved connector that does not lessen the impedance characteristics of connected wire pairs and minimizes common mode (CM) noise that occurs from typical cancellator/compensation circuits. These and other needs are addressed by the systems and methods of the present disclosure.


There is provided a print apparatus which prints a plurality of pieces of linked document information of those that are distributed to and stored in a plurality of external document servers. The apparatus includes an extraction unit for extracting link information indicating second document information, which is linked to first document information, from the first document information received from the corresponding document server, a second reception unit for receiving the second document information indicated by the extracted link information from the corresponding document server, a print unit for assigning serial page numbers to the first document information and the second document information, and printing the first document information and the second document information, and a recurring information detection unit for detecting that the already printed second document information is linked again to the first document information. Hypermedia documents are printed in the form that it is easy for the user to use.

1. Field of the Invention
The present invention relates to an information print apparatus and method for printing information of a digital document such as a hypermedia document, or the like.
2. Description of the Related Art
In recent years, with the spread of computers and network environments, more documents are created and managed in offices not as orthodox paper documents but as digital documents using wordprocessors or the like. Digital documents used in such environment offer new application methods that utilize convenient features unlike orthodox paper documents.
For example, hypermedia documents built on World Wide Webs (WWWs) using, e.g., the Internet are stored at different locations in units of information topics in a plurality of document servers that are distributed on the network and operate independently. More specifically, unlike in a conventional method that linearly manages an information group like a conventional paper document in units of "pages", information is managed nonlinearly. In order to look up hypermedia documents, a user acquires information by connecting to document servers corresponding to required "topics", and prepares the entire document on the user's side. For example, in an on-demand print method which is receiving a lot of attention in recent years, information corresponding to a user's request is read out from each document server, and is printed in the order requested by the user.
Upon printing document information such as wordprocessor documents which are stored in one or a plurality of files, a document is printed by designating pages, and is not linked with other documents. WWW hypermedia documents and the like are separately stored in units of topics, as described above, and only a required topic is printed upon request.
More specifically, since paper documents are linearly managed by a sequence of page numbers, and hypermedia documents are nonlinearly managed by links among topics, printing a hypermedia document is a conversion from nonlinear information to linear information.
FIG. 14 is a functional block diagram showing the module arrangement associated with such digital document print apparatus. More specifically, this print apparatus is constituted by a user input unit 90, an information storage unit 91, a link information management unit 92, an information reception unit 94 which is connected to a network line 8 and receives information from an external document server, a link information extraction unit 95, a print buffer memory 96, and a print unit 97 which has a page number management unit (not shown) and controls the print buffer memory 96. The print unit 97 informs a printer 98 of the presence of printable information in the print buffer memory 96, and the printer 98 prints the information.
The print operation in the digital document print apparatus with the above arrangement will be described below with reference to the flow chart shown in FIG. 15.
The information reception unit 94 forms a message as a transmission request of stored information with respect to the storage location of document information input and designated by the user input unit 90, and transmits the message via the network line 8. The information reception unit 94 waits until the requested document information is transmitted. Upon reception of the information, the information reception unit 94 transfers the received information to the information storage unit 91, which informs the print unit 97 that the new information is stored.
The print unit 97 writes the document information in the print buffer memory 96 in units of print pages, and assigns page numbers. The print unit 97 informs the printer 98 of the presence of printable information in the print buffer memory 96, and the printer 98 prints information for one page stored in the print buffer memory 96.
Upon completion of printing up to the last page, the page number management unit of the print unit 97 resets the page number to 0, and ends processing.
When a digital document is to be processed in such network environment, the user reads out some pieces of information associated with desired topics and selectively prints them upon looking up nonlinearly managed information distributed on the network.
However, when the print apparatus prints information by tracking links among those pieces of information, there are a very large number of information links including links to identical, recurring information, and hence, such print method may often pose a problem.
For example, when information which is being displayed is to be printed, the Mosaic software as a popular WWW viewer prints only an "information page" (corresponding to the above-mentioned topic) which is read out at that time, but does not print another information page to which this information page is linked. When the user wants to print another information page, he or she must display the information and determine whether or not he or she wants to print the displayed information.
When nonlinearly stored information is converted into linear information, and the converted information is printed, the print order may often pose a problem. That is, the converted linear information may be printed in an inappropriate order, and may have contents which are not easy to understand. On the other hand, identical information may recur upon tracking information links, and paper sheets may be wasted if information is printed in every such occasions. Furthermore, an access error to information may often lead to a print instruction error, and cannot often be reflected in the print result.


Triazolone derivatives represented by the formula

The present invention relates to triazolone derivatives, use thereof, and intermediates therefor.
An object of the present invention is to provide compounds having excellent plant disease control activity.
As a result of the present inventors"" intensive study, it has been found that triazolone derivatives represented by the following formula [I] have excellent plant disease control activity. Thus, the present invention has been completed.
That is, the present invention provides a triazolone derivative represented by the formula [I]
wherein
R1 represents optionally substituted C1-10 alkyl, optionally substituted C2-10 alkenyl, optionally substituted C2-10 alkynyl, halogen (chlorine, bromine, iodine or fluorine), nitro, cyano, optionally substituted C3-10 cycloalkyl, optionally substituted C4-20 cycloalkylalkyl, optionally substituted C5-10 cycloalkenyl, optionally substituted C6-20 cycloalkenylalkyl, optionally substituted C6-10 aryl, optionally substituted C7-20 arylalkyl, optionally substituted C1-9 heteroaryl, optionally substituted C2-19 heteroarylalkyl, A1xe2x80x94L1xe2x80x94, A1xe2x80x94ONxe2x95x90CA2xe2x80x94, A1xe2x80x94ONxe2x95x90C(Me)CH2ONxe2x95x90CA2xe2x80x94, A1C(A2)xe2x95x90NOCH2xe2x80x94, A1SC(A2)xe2x95x90Nxe2x80x94, A1C(xe2x95x90S)NHxe2x80x94, A1SC(xe2x95x90S)NHxe2x80x94, A1SC(SA2)xe2x95x90Nxe2x80x94, A1xe2x80x94ONxe2x95x90C(CN)xe2x80x94, A1xe2x80x94ONxe2x95x90C(Me)CH2ONxe2x95x90C(CN)xe2x80x94, or A1C(CN)xe2x95x90NOCH2xe2x80x94 (wherein L1 represents oxygen, sulfur, carbonyl, xe2x80x94OCH2xe2x80x94, xe2x80x94SCH2xe2x80x94, xe2x80x94C(xe2x95x90O)Oxe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90O)OCH2xe2x80x94, xe2x80x94NHxe2x80x94, or C1-6 alkylimino; A1 and A2 are the same or different, and each represents optionally substituted C1-10 alkyl, optionally substituted C2-10 alkenyl, optionally substituted C2-10 alkynyl, optionally substituted C3-10 cycloalkyl, optionally substituted C4-20 cycloalkylalkyl, optionally substituted C5-10 cycloalkenyl, optionally substituted C6-20 cycloalkenylalkyl, optionally substituted C6-10 aryl, optionally substituted C7-20 arylalkyl, hydrogen, optionally substituted C1-9 heteroaryl, or optionally substituted C2-19 heteroarylalkyl);
R2 represents hydrogen, or C1-6 alkyl;
R3 represents C1-6 alkoxy, C1-6 alkylthio, cyano, halogen, vinyl, ethynyl, cyclopropyl, or C1-6 alkyl;
one of T, U and V represents CR4, another one represents CH or nitrogen, and the remaining one represents CR5 or nitrogen; and
W represents CR6 or nitrogen;
(wherein R4, R5 and R6 are the same or different, and each represents hydrogen, halogen, C1-6 alkyl, C1-6 alkoxy, C1-6 haloalkyl, C1-6 haloalkoxy, cyano, nitro, C2-6 alkoxycarbonyl, C1-6 alkylthio, or C1-6 haloalkylthio) (hereinafter referred to as the compound of the present invention). Further, the present invention provides an agricultural or horticultural fungicide composition comprising as an active ingredient the compound of the present invention.
The present invention also provides intermediates useful for producing (a part of) the compound of the present invention, that is, an alkoxytriazolone compound represented by the formula [II-1]
wherein
R31 represents C1-6 alkyl (e.g., methyl, ethyl, etc.);
a boron compound represented by the formula [III-1]
xe2x80x83wherein both R14 bind to each other at the terminal ends thereof to represent ethylene or trimethylene (they may be substituted with one or more methyl or phenyl, respectively) (e.g., xe2x80x94C(CH3)2xe2x80x94C(CH3)2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2xe2x80x94C(CH3)2xe2x80x94CH2xe2x80x94, xe2x80x94CH(Ph)xe2x80x94CH2xe2x80x94CH(Ph)xe2x80x94, etc.), or it represents C1-6 alkyl (e.g., methyl, ethyl, isopropyl, etc.) or hydrogen; and R2, R3, V, U, T and W are as defined above; and
a triazolone compound represented by the formula [IV]
xe2x80x83wherein R1, R2, R3, V, U, T and W are as defined above.
In the present invention, as the C1-10 alkyl of the optionally substituted C1-10 alkyl represented by R1, A1 and A2, for example, there are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 1-methylpropyl, pentyl, 1-methylbutyl, 1-ethylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, hexyl, 1-methylpentyl, 1-ethylpentyl, 3,3-dimethylbutyl, heptyl, 3,7-dimethyloctyl, and the like.
As the C2-10 alkenyl of the optionally substituted C2-10 alkenyl represented by R1, A1 and A2, for example, there are vinyl, allyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-butenyl, and the like.
As the C2-10 alkynyl of the optionally substituted C2-10 alkynyl represented by R1, A1 and A2, for example, there are ethynyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, and the like.
As the halogen represented by R1, there is chlorine, bromine, iodine or fluorine.
As the C3-10 cycloalkyl of the optionally substituted C3-10 cycloalkyl represented by R1, A1 and A2, for example, there are cyclopropyl, cyclopentyl, cyclohexyl, and the like.
As the C4-20 cycloalkylalkyl of the optionally substituted C4-20 cycloalkylalkyl represented by R1, A1 and A2, for example, there are cyclopropylmethyl, cyclopentylmethyl, 2-cyclopentylethyl, cyclohexylmethyl, and the like.
As the C5-10 cycloalkenyl of the optionally substituted C5-10 cycloalkenyl represented by R1, A1 and A2, for example, there are cyclopentenyl, cyclohexenyl, and the like.
As the C6-20 cycloalkenylalkyl of the optionally substituted C6-20 cycloalkenylalkyl represented by R1, A1 and A2, for example, there are cyclopentene-1-ylmethyl, cyclohexene-1-ylmethyl, and the like.
As the C6-10 aryl of the optionally substituted C6-10 aryl represented by R1, A1 and A2, for example, there are phenyl, xcex1-naphthyl, xcex2-naphthyl, and the like.
As the C7-20 arylalkyl of the optionally substituted C7-20 arylalkyl represented by R1, A1 and A2, for example, there are phenylmethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, xcex1-naphthylmethyl, xcex2-naphthylmethyl, and the like.
As the C1-9 heteroaryl of the optionally substituted C1-9 heteroaryl represented by R1, A1 and A2, for example, there are 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 3-pyridazinyl, 4-pyridazinyl, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1-(1,2,4-triazolyl), 3-(1,2,4-triazolyl), 4-(1,2,4-triazolyl), 2-benzothienyl, 3-benzothienyl, benzothiazol-2-yl, 2-quinolinyl, and the like.
As the C2-19 heteroarylalkyl of the optionally substituted C2-19 heteroarylalkyl represented by R1, A1 and A2, for example, there are 2-pyridylmethyl, 4-pyridylmethyl, 2-pyrimidinylmethyl, 4-pyrimidinylmethyl, 3-pyrazolylmethyl, 2-thiazolylmenthyl, 2-imidazolylmethyl, 3-(1,2,4-triazolyl)methyl, 2-quinolinylmethyl, and the like.
As the substituents of the optionally substituted C1-10 alkyl, optionally substituted C2-10 alkenyl, optionally substituted C2-10 alkynyl, optionally substituted C3-10 cycloalkyl, optionally substituted C4-20 cycloalkylalkyl, optionally substituted C5-10 cycloalkenyl, optionally substituted C6-20 cycloalkenylalkyl, optionally substituted C6-10 aryl, optionally substituted C7-20 arylalkyl, optionally substituted C1-9 heteroaryl, or optionally substituted C2-19 heteroarylalkyl represented by R1, A1 and A2, for example, there are:
halogen (chlorine, bromine, fluorine, etc.);
C1-10 alkyl (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 1-methylpropyl, pentyl, 1-methylbutyl, 1-ethylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, hexyl, 1-methylpentyl, 1-ethylpent yl, 3,3-dimethylbutyl, heptyl, 3,7-dimethyloctyl, etc.);
C3-20 trialkylsilyl (e.g. , trimethylsilyl, is triethylsilyl, etc.);
C1-10 haloalkyl (e.g., trifluoromethyl, 2,2,2-trifluoroethyl, b,1,2,2-tetrafluoroethyl, etc.);
C3-10 cycloalkyl (e.g., cyclopropyl, cyclopentyl, cyclohexyl, etc.);
C1-10 alkoxy (e.g., methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, n-pentyloxy, etc.);
C1-10 haloalkoxy (e.g., trifluoromethoxy, difluoromethoxy, bromodifluoromethoxy, chlorodifluoromethoxy, fluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, etc.);
C1-10 alkylthio (e.g., methylthio, ethylthio, n-propylthio, n-butylthio, isobutylthio, sec-butylthio, n-pentylthio, n-hexylthio, etc.);
C1-10 haloalkylthio (e.g., trifluoromethylthio, difluoromethylthio, bromodifluoromethylthio, chlorodifluoromethylthio, fluoromethylthio, 2,2,2-trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio, etc.);
C2-10 alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonayl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, etc.);
phenyl; phenoxy; benzyloxy; phenoxymethyl; C1-9 heteroaryl; (C1-9 heteroaryl)methyloxy; (C1-9 heteroaryl)oxymethyl; C1-9 heteroaryloxy [wherein each of the phenyl, phenoxy, benzyloxy, phenoxymethyl, C1-9 heteroaryl, (C1-9 heteroaryl)methyloxy, (C1-9 heteroaryl)oxymethyl, and C1-9 heteroaryloxy may be substituted with one or more substituents selected from the group consisting of halogen (e.g., chlorine, etc.), C1-6 alkyl (e.g., methyl, ethyl, etc.), C1-6 alkoxy (e.g., methoxy, ethoxy, etc.), trifluoromethyl, and cyano; and examples of the C1-9 heteroaryl of the C1-9 heteroaryl, (C1-9 heteroaryl)methyloxy, (C1-9 heteroaryl)oxymethyl and C1-9 heteroaryloxy include 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 3-pyridazinyl, 4-pyridazinyl, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1-(1,2,4-triazolyl), 3-(1,2,4-triazolyl), 4-(1,2,4-triazolyl), 2-benzothienyl, 3-benzothienyl, benzothiazol-2-yl, 2-quinolinyl, and the like];
methylenedioxy and difluoromethylenedioxy (each of the methylenedioxy and difluoromethylenedioxy is attached to the two adjacent carbon atoms of the aryl moiety);
hydroxyl; cyano; and nitro.
As the C1-6 alkyl represented by R2 and R31, for example, there are methyl, ethyl, and the like.
As the C1-6 alkoxy represented by R3, for example, there are methoxy, ethoxy, and the like.
As the C1-6 alkylthio represented by R3, for example, there are methylthio, ethylthio, and the like.
As the halogen represented by R3, for example, there are chlorine, bromine, iodine, fluorine, and the like.
As the C1-6 alkyl represented by R3, for example, there are methyl, ethyl, and the like.
As the halogen represented by R4, R5 and R6, for example, there are chlorine, bromine, fluorine, and the like.
As the C1-6 alkyl represented by R4, R5 and R6, for example, there are methyl, ethyl, and the like.
As the C1-6 alkoxy represented by R4, R5 and R6, for example, there are methoxy, ethoxy, and the like.
As the C1-6 haloalkyl represented by R4, R5 and R6, for example, there are trifluoromethyl, and the like.
As the C1-6 haloalkoxy represented by R4, R5 and R6, for example, there are trifluoromethoxy, difluoromethoxy, bromodifluoromethoxy, chlorodifluoromethoxy, fluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, and the like.
P As the C2-6 alkoxycarbonyl represented by R4, R5 and R6, for example, there are methoxycarbonyl, ethoxycarbonyl, and the like.
As the C1-6 alkylthio represented by R4, R5 and R6, for example, there are methylthio, ethylthio, and the like.
As the C1-6 haloalkylthio represented by R4, R5 and R6, for example, there are trifluoromethylthio, difluoromethylthio, bromodifluoromethylthio, chlorodifluoromethylthio, fluoromethylthio, 2,2,2-trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio, and the like.
Specific examples of 6 membered aromatic ring containing T, U, V and W include benzene ring, pyridine ring and pyrimidine ring.
The compound of the present invention may be present in the form of its (E) isomer and (Z) isomer with respect to its Cxe2x95x90N bond and/or Cxe2x95x90C bond. The present invention includes both respective isomers and a mixture thereof. (The terms (E) and (Z) used herein are those used for broadly defining geometrical isomers according to Cahn-Ingold-Prelog convention.) In the compounds of the present invention, from the viewpoint of plant disease control activity, the preferred substituents are optionally substituted phenyl as R1, hydrogen as R2, and methoxy as R3.
In the compounds of the present invention, from the viewpoint of plant disease control activity, the preferred 6-membered aromatic ring moiety containing T, U, V and W is that wherein T is CMe, U is CH, V is CH and W is CH.
Among the compounds of the present invention, from the viewpoint of plant disease control activity, examples of the preferred compounds include
5-methoxy-2-methyl-4-(2-methyl-5-phenylbenzyl)-2,4-dihydro-3H-1,2,4-triazol-3-one (the compound of the present invention No. 6), and
4-{5-(3,3-dimethyl-1-butynyl)-2-methylbenzyl}-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (the compound of the present invention No. 526).
The compounds of the present invention can be produced according to, for example, the following Process Axe2x80x94Process E, and Process G. Further, the desired R1 can be introduced or constructed in the final step depending upon a particular R1 (e.g., Process F). In these processes, a protective group can be used for protecting a functional group from a reaction, if necessary.
As seen from the following Processes and Production Examples, among the compounds of the present invention, a part thereof, i.e., the chlorotriazoline compound represented by the formula [I-1] (Process A), the compounds represented by the formulas [I-2-1], [I-2], [I-5], [I-6], [I-5-1], [I-8], and [I-9] {Process F (Schemes 6, 7, 9, 10, and 11}, and the compound represented by the formula [I-18] {Process G (Scheme 14)} are also useful as intermediates for producing the other compounds of the present invention.
Process A: the production of the compound of the present invention wherein R3 is C1-6 alkoxy, C1-6 alkylthio, cyano, fluorine, bromine, or iodine
In this process, a chlorotriazolone compound represented by the formula [I-1]
wherein
R1, R2, T, U, V and W are as defined above, is reacted with a compound of the formula [V]
R34-M
wherein R34 is C1-6 alkoxy, C1-6 alkylthio, cyano, fluorine, bromine, or iodine; and M represents an alkali metal (e.g., sodium, potassium, lithium, cesium, etc.).
Specific examples of the compound represented by the formula [V] include sodium methoxide, sodium ethoxide, sodium thiomethoxide, sodium thioethoxide, sodium cyanate, potassium cyanate, potassium fluoride, sodium bromide, etc.
Normally, the reaction temperature of this reaction is in the range of xe2x88x9220 to 200xc2x0 C. and the reaction time is in the range of 1 to 100 hours.
Normally, in this reaction, the compound represented by the formula [V] is used at the ratio of 1 to 100 mole per 1 mole of the chlorotriazolone compound represented by the formula [I-1].
Normally, this reaction is carried out by using a solvent. Examples of the solvent include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl ether, tert-butyl methyl ether, etc.; aliphatic hydrocarbons such as n-hexane, heptane, ligroin, petroleum ether, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; alcohol such as methanol, ethanol, etc.; N,N-dimethylformamide; N,N-dimethylacetamide; dimethylsulfoxide; water, etc.; or a mixture thereof.
After completion of the reaction, the reaction U mixture can be subjected to a work-up procedure such as extraction with an organic solvent, concentration, etc. to isolate the desired compound. The compound can also be purified by recrystallization, chromatography, etc.
The chlorotriazolone compound represented by the formula [I-1] can be produced, for example, as follows (Process B).
Process B: the production of the compound of the present invention wherein R3 is chlorine.
In this process, the semicarbazide compound represented by the formula [VI]
wherein R1, R2, T, U, V and W are as defined above, is reacted with triphosgene [bis(trichloromethyl)carbonate], diphosgene (trichloromethyl chloroformate) or phosgene.
Normally, the reaction temperature of this reaction is in the range of xe2x88x9220 to 150xc2x0 C. and the reaction time is in the range of 1 to 100 hours.
Normally, in this reaction, triphosgene, diphosgene or phosgene is used at the ratio of 1 to 100 mole per 1 mole of the semicarbazide compound represented by the formula [VI].
If necessary, this reaction is carried out by using a solvent. Examples of the solvent include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether, etc.; aliphatic hydrocarbons such as n-hexane, heptane, ligroin, petroleum ether, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene, etc.; or a mixture thereof.
After completion of the reaction, the reaction mixture can be subjected to a work-up procedure such as extraction with an organic solvent, concentration, etc., to isolate the desired compound. The compound can be purified by recrystallization, chromatography, etc.
The seimicarbazide compound represented by the formula [VI] can be produced by, for example, according to the following Scheme 1.
wherein R1, R2, T, U, V and W are as defined above; R21 represents C1-4 alkyl (e.g., methyl, ethyl, etc.); M1 represents silver or sodium; L represents a leaving group such as chlorine, bromine, iodine, p-toluenesulfonyloxy, methanesulfonyloxy, trifluoromethanesulfonyloxy, etc.; DIBAH represents diisobutylaluminum hydride; BuLi represents butyllithium; and DMF represents N,N-dimethylformamide.
The reaction for producing the compound represented by the formula [VII] by reacting the compound represented by the formula [XII] with diphosgene or phosgene can be carried out according to, for example, the process described in J. Org. Chem., 61, 3883-3884 (1996).
Process C
In this process, a triazolone compound represented by the formula [IV]
wherein
R1, R2, R3, T, U, V and W are as defined above, is reacted with a methylating agent represented by the formula [XV]
CH3xe2x80x94L2
wherein L2 represents a leaving group such as chlorine, bromine, iodine, p-toluenesulfonyloxy, methanesulfonyloxy, trifluoromethanesulfonyloxy, OSO2OCH3, etc.
Normally, this reaction is carried out in the presence of a base. Examples of the base to be used include inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.
Normally, the reaction temperature of this reaction is in the range of xe2x88x9220 to 150xc2x0 C. and the reaction time is in the range of 1 to 100 hours.
Normally, in this reaction, the methylating agent represented by the formula [XV] and the base are used at the ratios of 1 to 5 mole, and 1 to 10 mole per 1 mole of the triazolone compound represented by the formula [IV], respectively.
If necessary, this reaction can be carried out by using a solvent. Examples of the solvent include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether, etc.; aliphatic hydrocarbons such as n-hexane, heptane, ligroin, petroleum ether, etc.; aromatic hydrocarbons toluene, xylene, etc.; organic bases such as pyridine, triethylamine, N-methylaniline, N,N-dimethylaniline, N,N-diethylaniline, etc.; nitrites such as acetonitrile, isobutyronitrile, etc.; N,N-dimethylformadmide; dimethylsulfoxide; water; etc., or a mixture thereof.
After completion of the reaction, the reaction mixture can be subjected to a work-up procedure such as extraction with an organic solvent, concentration, etc. to isolate the desired compound. This compound can also be purified by recrystallization, chromatography, etc.
The triazolone compound of the formula [IV] can be produced, for example, by the process according to the following Scheme 2.
wherein R1, R2, R3, T, U, V, W and L are as defined above.
Normally, this reaction is carried out in the presence of a base (e.g., sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.).
The compound represented by the formula [XVI] is a known compound described in, for example, JP 8-325244 A; J. Chem. Soc. Perkin I, 2644-2646 (1973); Chem. Ber. 102, 755-766 (1969); Chem. Ber. 98, 3025-3033 (1965), etc., or it can be produced according to the process described therein, or it can be produced from the compound described therein.
Among the triazolone compounds represented by the formula [IV], those wherein R3 is C1-6 alkyl or cyclopropyl can be produced according to the process of the following Scheme 3.
wherein R33 represents C1-6 alkyl (e.g., methyl, ethyl, etc.) or cyclopropyl; and R1, R2, T, U, V and W are as defined above. Examples of the base include an aqueous solution of potassium hydroxide, etc.
Process D
In this process, a compound represented by the formula [II]
wherein R3 is as defined above (including the alkoxytriazolone compound represented by the formula [II-1]), is reacted with the compound represented by the formula [VIII] in Scheme 1.
Normally, this reaction is carried out in the presence of a base. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, etc.; organic bases such as pyridine, 2-picoline, 4-picoline, 4-dimethylaminopyridine, quinoline, triethylamine, ethyldiisopropylamine, N, N-dimethylaniline, N, N-diethylaniline, etc.; or a mixture thereof.
Normally, the reaction temperature of this reaction is in the range of xe2x88x9220 to 150xc2x0 C. and the reaction time is in the range of 1 to 100 hours.
Normally, in this reaction, the compound represented by the formula [VIII] and the base are used at the ratios of 0.5 to 2 mole, and 0.5 to 4 mole per 1 mole of the triazolone represented by the formula [II], respectively.
If necessary, this reaction can be carried out by using a solvent. The solvent is selected according to the base used and examples of the solvent include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether, etc.; aliphatic hydrocarbons such as n-hexane, heptane, ligroin, petroleum ether, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; organic bases such as pyridine, triethylamine, N-methylaniline, N,N-dimethylaniline, N,N-diethylaniline, etc.; nitrites such as acetonitrile, isobutyronitlie, etc.; N,N-dimethylformamide; dimethylsulfoxide; water; etc., or a mixture thereof.
After completion of the reaction, the reaction mixture can be subjected to a work-up procedure such as extraction with an organic solvent, concentration, etc. to isolate the desired compound. This compound can also be purified by recrystallization, chromatography, etc.
The triazolone represented by the formula [II] is a known compound described in, for example, Chem. Ber. 102, 755-766 (1969); Chem. Ber. 98, 3025-3033 (1965); etc., or it can be produced by the process described therein or the method described in JP 8-325244 A, or it can be produced from the compound described therein.
The alkoxytriazolone compound represented by the formula [II-1] can be produced, for example, according to the following Scheme 4.
wherein X1 represents bromine or chlorine; R31 is as defined above, R32 represents C1-6 alkyl (e.g., methyl, ethyl, etc.).
That is, the alkoxytriazolone compound represented by the formula [II-1] can be produced by cyclizing the isosemicarbazide compound represented by the formula [XXIII] or a tautomer compound thereof normally at 20 to 150xc2x0 C. normally in the presence of sodium alkoxide represented by the formula [XXIV] (e.g., sodium methoxide, sodium ethoxide, etc.), followed by treatment with an acid (e.g., hydrochloric acid, etc.).
The isosemicarbazide compound represented by the formula [XXIII] can be produced by reacting the dialkyl iminocarbonate represented by the formula [XXII] with carbazate derivative represented by the formula [XIX] normally at xe2x88x9220 to 120xc2x0 C. normally in the presence of a catalyst (e.g., protonic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, acetic acid, propionic acid, pivalic acid, methanesulfonic acid, etc.).
For example, the dialkyl iminocarbonate represented by the formula [XXII] can be produced by reacting a cyanogen halide represented by the formula [XX] (cyanogen bromide or cyanogen chloride) with sodium alkoxide represented by the formula [XXIV] (e.g., sodium methoxide, sodium ethoxide, etc.) normally at xe2x88x9220 to 50xc2x0 C., followed by treatment with an acid (e.g., hydrochloric acid, etc.).
The carbazate derivative represented by the formula [XIX] can be produced by reacting alkyl chlorocarbonate represented by the formula [XVIII] with methyl hydrazine normally at xe2x88x9220 to 50xc2x0 C., if necessary, in the presence of acid trapping agent.
Process E: the production of the compound of the present invention wherein R3 is C1-6 alkyl or cyclopropyl In this process, the compound represented by the formula [XXV]
wherein R1, R2, R33, T, U, V and W are as defined above is cyclized and dehydrated.
Normally, this reaction is carried out in the presence of a base and examples of the base include inorganic bases such as potassium hydroxide, sodium hydroxide, etc.
Normally, the reaction temperature of this reaction is in the range of xe2x88x9220 to 150xc2x0 C. and the reaction time is in the range of 1 to 100 hours.
Normally, in this reaction, the base is used at the ratio of 1 to 10 mole per 1 mole of the compound represented by the formula [XXV].
If necessary, this reaction can be carried out by using a solvent. Examples of the solvent include water; ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether, etc.; aliphatic hydrocarbons such as n-hexane, heptane, ligroin, petroleum ether, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; or a mixture thereof.
After completion of the reaction, if necessary, the reaction mixture can be acidified and then subjected to a work-up procedure such as extraction with an organic solvent, concentration, etc. to isolate the desired compound. The compound can also be purified by recrystallization, chromatography, etc.
The compound represented by the formula [XXV] can be produced, for example, according to the following process of Scheme 5.
wherein R1, R2, R31, T, U, V and W are as defined above.
Process F
For example, there are the following F-1 to F-6.
F-1
This is the process according to Scheme 6.
wherein X2 represents bromine or iodine; R2, R3, T, U, V and W are as defined above; and the group represented by the formula Axe2x80x94Cxe2x89xa1Cxe2x80x94H represents optionally substituted C2-10 alkynyl having the triple bond at its terminal, and A represents the residue thereof; the substituent of the C2-10 alkynyl includes that of the above optionally substituted C2-10 alkynyl represented by R1.
This reaction can be carried out in the presence of a base [for example, a tertiary amine (e.g., triethylamine, diisopropylethylamine, etc.), a secondary amine (diethylamine, etc.), a primary amine (e.g., butylamine, etc.) or the like] and a catalyst [for example, a palladium catalyst (e.g. palladium (II) acetate, tetrakis(triphenylphosphine)palladium (0), bis(triphenylphosphine)palladium (II) dichloride (PdCl2(PPh3)2, etc.) and, if necessary, copper (I) iodide and triphenylphosphine, etc.] in an aprotic polar solvent (e.g., acetonitrile, N,N-dimethylformamide, etc.) [more specifically, according to the method described in Example 1 of WO98/03464, that described in Tetrahedron Lett., 1975, 4467, that described in Synthesis, 1980, 627, or the like].
F-2
This is the process according to Scheme 7.
wherein X represents bromine, iodine, chlorine or trifluoromethanesulfonyl; Z represents B(OR14) or SnR153; R15 represents C1-4 alkyl (e.g., methyl, ethyl, butyl, etc.); A3 represents optionally substituted C6-10 aryl or optionally substituted C1-9 heteroaryl; and R2, R3, R14, T, U, V and W are as defined above.
Normally, the reaction temperature is in the range of 20 to 120xc2x0 C., the reaction time is in the range of 1 to 24 hours and the compound represented by the formula [XXVI] is used at the ratio of 0.8 to 5 mole per 1 mole of the compound represented by the formula [I-2].
Normally, this reaction is carried out by using 0.001 to 0.1 mole of the catalyst per 1 mole of the compound represented by the formula [I-2]. Examples of the catalyst include palladium catalysts such as palladium (II) acetate, tetrakis (triphenylphosphine) palladium (0), {1,1xe2x80x2-bis(diphenylphosphino)ferrocene}dichloropalladium (II) methylene chloride complex, tris(dibenzylidene acetone)-(chloroform)-di-palladium (0) [Pd2(dba)3CHCl3], bis(triphenylphosphine)palladium (II) dichloride, etc.
If necessary, this reaction can also be carried out in the presence of a base (e.g., inorganic bases such as sodium acetate, potassium acetate, potassium carbonate, cesium carbonate, tripotassium phosphate, sodium bicarbonate, etc.), a phase-transfer catalyst (e.g., quaternary ammonium salts such as tetrabutylammonium bromide, benzyltriethylammonium bromide, etc.), a ligand (e.g., tri-tert-butylphosphine, etc.). Further, in case the compound represented by the formula [XXVII] wherein Z is SnR153, copper (II) oxide, silver (I) oxide, etc. can be used as a co-catalyst.
Normally, the reaction is carried out in a solvent. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol, etc.; ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, t-butyl methyl ether, etc.; aliphatic hydrocarbon solvents such as n-hexane, n-heptane, etc.; aromatic hydrocarbon solvents such as toluene, etc.; nitrile solvents such as acetonitrile, etc.; N,N-dimethylformamide; dimethylsulfoxide; water; etc., or a mixture thereof.
More specifically, this reaction can be carried out according to the process described in J. Org. Chem., 1997, 62, 7170-7173 [carried out in water in the presence of tetrabutylammonium bromide, a base (e.g., inorganic base such as potassium carbonate, etc.) and a catalyst (e.g., palladium (II) acetate, etc.)]; the process described in Beispiel 2 of WO96/35669 [carried out in a mixture of water and dimethoxyethane in the presence of a base (e.g., inorganic base such as sodium bicarbonate, etc.) and a catalyst (e.g., Pb(PPh3)4, etc.)]; the process described in J. Org. Chem., 1995, 60, 7508-7510; the process described in Angew. Chem. Int. Ed., 1998, 37 (24), 3387-3388; the process described in Angew. Chem. Int. Ed. Engl., 1986, 25, 508-524: or the like.
After completion of the reaction, the reaction mixture can be subjected to a conventional work-up procedure such as extraction with an organic solvent, concentration, etc. to obtain the desired compound. If necessary, the desired compound can be purified by recrystallization, chromatography, etc.
The compound represented by the formula [XXVII] is commercially available, or it can be produced by, for example, the process of the following Scheme 8.
wherein A3, X and Z are as defined above.
For example, the reaction can be carried out by a process wherein a Grignard reagent or organic lithium compound obtained by reacting the compound represented by the formula [XXVIII] with a metal (e.g., magnesium, lithium, etc.) or an organic lithium reagent (e.g., tert-butyllithium, n-butyllithium, lithium diisopropylamide, etc.) in a solvent (e.g., diethyl ether, tetrahydrofuran etc.) is reacted with a borate (e.g., trimethyl borate, triethyl borate, triisopropyl borate, etc.), if necessary, followed by hydrolysis (more specifically, carried out according to, for example, the process described in Organometallics, 1983, 2, 1316; Liebigs Ann., 1996, 1037; Jikken Kagaku Koza, 4th Ed., Vol. 24, Organic Synthesis VI, p 80, Maruzen;, J. Am. Chem., Soc., 1958, 80, 4291-4293); a process wherein the compound represented by the formula [XXVIII] is reacted with bis(pinacolate)diborone in a solvent (e.g., dimethylsulfoxide, N,N-dimethylformamide, etc.) in the presence of a base (e.g., inorganic base such as potassium acetate, etc.) and a catalyst (e.g., {1,1xe2x80x2-bis(diphenyphosphono)ferrocene}dichloropalladium (II) methylene chloride complex, etc.), if necessary, followed by hydrolysis (more specifically, carried out according to, for example, the process described in J. Org. Chem., 1995, 60, 7508-7510); a process wherein the compound represented by the formula [XXVIII] is reacted with R153SnSnR15 (e.g., Bu3SnSnBu3, etc.) in a solvent (e.g., toluene, etc.) in the presence of a catalyst (e.g., tetrakis(triphenylphosphine)-palladium (0), etc.) (more specifically, carried out according to, for example, the process described in Chem. Letters, 1981, 829-830); or the like.
After completion of the reaction, the reaction mixture can be subjected to a conventional work-up procedure such as extraction with an organic solvent, concentration, etc. to obtain the desired compound. If necessary, the desired compound can be purified and isolated by recrystallization, distillation, chromatography, etc.
F-3
This is the process according to the following Scheme 9.
wherein A11 represents A1 other than hydrogen, and A1, A2, R2, R3, L, T, U, V and W are as defined above.
Among the compounds represented by the formula [I-5], that wherein A2 is methyl can be produced according to, for example, the process described in J. Org. Chem., 1992, 57, 1481-1486 by reacting the compound represented by the formula [I-2] with butyl vinyl ether in the presence of a palladium catalyst, a phosphine ligand and a base, followed by acid hydrolysis.
F-4
This is the process according to the following Scheme 10.
wherein A1, A2, R2, R3, L, T, U, V and W are as defined above.
F-5
This is the process according to the following Scheme 11.
wherein X2, R2, R3, T, U, V and W are defined above.
This reaction can be carried out according to, for example, the process described in Synlett, 1994, 371-372.
F-6
This is the process according to the following Scheme 12.
wherein A3, X, Z, R2, R3, T, U, V and W are as defined above.
Normally, the reaction temperature is in the range of 20 to 120xc2x0 C., the reaction time is in the range of 1 to 24 hours, and the compound represented by the formula [XXX] is used at the ratio of 1 to 5 mole per 1 mole of the compound represented by the formula [III].
Normally, in this reaction, the catalyst is used at the ratio of 0.001 to 0.1 mole per 1 mole of the compound represented by the formula [III]. Examples of the catalyst include palladium (II) acetate, tetrakis(triphenylphosphine)palladium (0), {1,1xe2x80x2-bis(diphenylphosphino)ferrocene}dichloro-palladium (II) methylene chloride complex, tris(dibenzylideneacetone)-(chloroform)-di-palladium (0) [Pd2(dba)3CHCl3], bis(triphenylphosphine)palladium (II) dichloride, etc.
If necessary, this reaction can also be carried out in the presence of a base (e.g., inorganic bases such as sodium acetate, potassium acetate, potassium carbonate, cesium carbonate, tripotassium phosphate, sodium bicarbonate, etc.), a phase-transfer catalyst (e.g., quaternary ammonium salts such as tetrabutylammonium bromide, benzyltriethylammonium bromide, etc.), a ligand (e.g., tri-tert-butylphosphine, etc.). Further, in case the compound represented by the formula [XXX] wherein A3 is SnR153, copper (II) oxide, silver (I) oxide, etc. can be used as a co-catalyst.
Normally, the reaction is carried out in a solvent. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol, etc..; ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, t-butyl methyl ether, etc.; aliphatic hydrocarbon solvents such as n-hexane, n-heptane, etc.; aromatic hydrocarbon solvents such as toluene, etc.; nitrile solvents such as acetonitrile, etc.; N,N-dimethylformamide; dimethylsulfoxide; water; etc., or a mixture thereof.
More specifically, this reaction can be carried out according to the process described in J. Org. Chem., 1997, 62, 7170-7173 [carried out in water in the presence of tetrabutylammonium bromide, a base (e.g., inorganic base such as potassium carbonate, etc.) and a catalyst (e.g., palladium (II) acetate, etc.)]; the process described in Beispiel 2 of WO96/35669 [carried out in a mixture of water and dimethoxyethane in the presence of a base (e.g., inorganic base such as sodium bicarbonate, etc.) and a catalyst (e.g., Pb(PPh3)4, etc.)]; the process described in J. Org. Chem., 1995, 60, 7508-7510; the process described in Angew. Chem. Int. Ed., 1998, 37 (24), 3387-3388; the process described in Angew. Chem. Int. Ed. Engl., 1986, 25, 508-524: or the like.
After completion of the reaction, the reaction mixture can be subjected to a conventional work-up procedure such as extraction with an organic solvent, concentration, etc. to obtain the desired compound. If necessary, the desired compound can be purified and isolated by recrystallization, distillation, chromatography, etc.
The compound represented by the formula [III] can be produced by the process represented by the following Scheme 13.
wherein X, Z, R2, R3, T, U, V and W are as defined above.
In the reaction of Scheme 3, normally, the reaction temperature is in the range of 20 to 100xc2x0 C., the reaction time is in the range of 1 to 24 hours and the compound represented by the formula [XXIX] is used at the ratio of 1 to 5 mole pre 1 mole of the compound represented by the formula [I-2].
For example, this reaction can be carried out by a process wherein the compound represented by the formula [I-2] is reacted with bis(pinacolate)diborone, etc. in a solvent (e.g., dimethylsulfoxide, N,N-dimethylformamide, etc.) in the presence of a base (e.g., inorganic base such as potassium acetate, etc.) and a catalyst (e.g., {1,1xe2x80x2-bis(diphenyphosphono)ferrocene}dichloropalladium (II) methylene chloride complex, etc.) (more specifically, carried out according to, for example, the process described in J. Org. Chem., 1995, 60, 7508-7510); a process wherein the compound represented by the formula [I-2] is reacted with R153SnSnR15 (e.g., Bu3SnSnBu3, etc.) in a solvent (e.g., toluene, etc.) in the presence of a catalyst (e.g., tetrakis(triphenylphosphine)-palladium (0), etc.) (more specifically, carried out according to, for example, the process described in Chem. Letters, 1981, 829-830); or the like. Further, in case of the compound represented by the formula [III] wherein Z is B(OR14)2 and R14 is C1-6 alkyl, for example, the reaction can be carried out by a process wherein a Grignard reagent or organic lithium compound obtained by reacting the compound represented by the formula [I-2] with a metal (e.g., magnesium, lithium, etc.) or an organic lithium reagent (e.g., tert-butyllithium, n-butyllithium, lithium diisopropylamide, etc.) in a solvent (e.g., diethyl ether, tetrahydrofuran etc.) is reacted with a tri-C1-6 aklyl borate (e.g., trimethyl borate, triethyl borate, triisopropyl borate, etc.), if necessary, followed by hydrolysis (more. specifically, carried out according to, for example, the process described in Organometallics, 1983, 2, 1316; Liebigs Ann., 1996, 1037; Jikken Kagaku Koza, 4th Ed., Vol. 24, Organic Synthesis VI, p 80, Maruzen; J. Am. Chem., Soc., 1958, 80, 4291-4293).
After completion of the reaction, the reaction mixture can be subjected to a conventional work-up procedure such as extraction with an organic solvent, concentration, etc. to obtain the desired compound. If necessary, the desired compound can be purified by recrystallization, chromatography, etc.
Process G
This process is carried out according to the following Scheme 14.
wherein TMS represents trimethylsilyl; and X, R1, R2, T, U, V and W are as defined above. Examples of the dehydrating agent include acetic anhydride, etc. Examples of the reducing agent include Lindlar catalyst, etc. Examples of the strong base include butyllithium, etc. Examples of the catalyst include palladium catalysts such as palladium (II) acetate, tetrakis(triphenylphosphine)palladium (0), bis(triphenylphosphine)palladium (II) dichloride (PdCl2(PPh3)2), etc. and, if necessary, copper (I) iodide and triphenylphosphine, etc.
The compound represented by the formula [XXXI] in Scheme 14, can be produced according to, for example, the following Scheme 15.
wherein A3, L1, X, Y, R6, R7 and R8 are as defined above. Examples of the base include an aqueous solution of potassium hydroxide, etc. Examples of the methylating agent include methyl iodide-potassium carbonate, etc. Examples of the oxidizing agent include maganese dioxide, etc.
When the compound of the present invention is used as an active ingredient of an agricultural or horticultural fungicide composition, it can be used as it is without addition of any other ingredient. However, normally, it is used in admixture with solid or liquid carriers, surfactants and other supplemental agents into conventional formulations such as emulsifiable concentrates, wettable powders, suspensions, water-dispersible granules, emulsions, dusts, granules, powders, granules, and the like. These formulations normally contain as an active ingredient 0.1 to 90% by weight of the compound of the present invention based on the total weight of the formulations.
Examples of the solid carrier to be used for such formulations include finely divided powder or granules of kaolin clay, attapulgite clay, bentonite, terra alba, pyrophyllite, talc, diatomaceous earth, calcite, corn rachis powder, walnut shell powder, urea, ammonium sulfate, synthesized hydrous silicon hydroxide, etc. Examples of the liquid carrier include aromatic hydrocarbons such as xylene, methylnaphthalene, etc.; alcohol such as isopropanol, ethylene glycol, Cellosolve(trademark), etc.; ketones such as acetone, cyclohexanone, isophorone, etc.; vegetable oils such as soybean oil, cottonseed oil, etc.; dimethylsulfoxide; acetonitrile; water; etc.
Examples of the surfactant include anion surfactants such as alkylsulfate salts, aklylarylsulfonate salts, dialkylsulfosuccinate salts, salts of phosphates of polyoxyethylene alkylaryl ethers, naphthlenesulfonate formalin condensate, etc.; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl polyoxypropylene block copolymers, sorbitan fatty acid esters. etc.; and the like.
Examples of the supplemental agent include ligninsulfonates, alginates, polyvinyl alcohol, gum arabic, carboxymethyl cellulose (CMC), isopropyl acid phosphate (PAP), etc.
The compound of the present invention can be applied by foliar application, soil treatment, seed disinfection, etc. as well as any other commonly utilized application method.
When the compound of the present invention is used as an active ingredient of an agricultural or horticultural fungicide composition, the dosage thereof is varied depending upon a particular kind of subject plant (crop, etc.), kind of objective plant disease, degree of disease, formulation type, application timing, weather conditions, etc. However, normally, the dosage is 0.01 to 50 g, preferably, 0.05 to 10 g per 1 are.
In case of applying emulsifiable concentrates, wettable powders, suspensions, emulsions, or the like by diluting it with water, the dosage concentration thereof is 0.0001 to 3%, preferably 0.0005 to 1%. The dusts, granules, etc. are applied as they are without dilution.
The compound of the present invention can be used as an agricultural or horticultural fungicide for fields, paddy fields, orchards, tea gardens, meadows, lawns and the like, and it is expected to enhance its fungicidal activity by using in admixture with other agricultural or horticultural fungicides. Examples of the other agricultural or horticultural fungicides which can be admixed with the compound of the present invention include azole fungicide compounds such as propiconazole, triadimenol, prochloraz, penconazole, tebuconazole, flusilazole, diniconazole, bromuconazole, epoxiconazole, difenoconazole, cyproconazole, metconazole, triflumizole, tetraconazole, myclobutanil, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, bitertanoal, imazalil, flutoriafol, etc.; cyclic amine fungicide compounds such as fenpropimorph, tridemorph, fenpropidin, etc.; benzimidazole fungicide compounds such as carbendazim, benomyl, thiabendazole, thiophanate-methyl, etc.; procymidone; cyprodinil; pyrimethanil; diethofencarb; thiram; fluazinam; mancozeb; iprodione; vinclozolin; chlorothalonil; captan; mepanipyrim; fenpiclonil; fludioxonil; dichlofluanid; folpet; kresoxim-methyl; azoxystrobin; N-methyl-xcex1-methoxyimino-2-[(2,5-dimethylphenoxy)methyl]phenylacetamide, spiroxamine; quinoxyfen; fenhexamid; fenamidone (RP-407213); iprovalicarb; and the like.
The compound of the present invention can also be used in admixture with or together with other agricultural or horticultural insecticides, acaricides, nematocides, herbicides, plant growth regulators, and fertilizers.
Examples of such insecticides and/or acaricides and/or nematocides include organic phosphorous compounds such as fenitrothion [O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate], fenthion [O,O-dimethyl O-(3-methyl-4-(methylthio)phenyl)phosphorothioate], diazinon [O,O-diethyl O-2-isopropyl-6-methylpyridin-4-ylphosphoro-thioate], chlorpyrifos [O,O-diethyl O-3,5,6-trichloro-2-pyridylphosphorothioate], acephate [O,S-dimethylacetyl-phosphoramidothioate], methidathion [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl O,O-dimethylphosphorothioate], disulfoton [O,O-diethyl S-2-ethylthioethylphosphorothioate], DDVP [2,2-dichlorovinyl-dimethylphosphate], sulprofos [O-ethyl O-4-(methylthio)phenyl S-propylphosphorodithioate], cyanophos [O-4-cyanophenyl O,O-dimethylphosphorothioate], dioxabenzofos [2-methoxy-4H-1,3,2-benzodioxaphosphinyn-2-sulfide], dimethoate [O,O-dimethyl S-(N-methylcarbamoylmethyl)-dithiophosphate], phenthoate [ethyl 2-dimethoxyphosphino-thioylthio(phenyl)acetate], malathion [diethyl(dimethoxyphosphinothioylthio)succinate], trichlorphon [dimethyl 2,2,2-trichloro-1-hydroxyehtylphosphpnate], azinphos-methyl [S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethyl O,O-dimethylphosphorodithioate], monocrotophos [dimethyl(E)-1-methyl-2-(methylcarbamoyl)vinylphosphate], ethion [O,O,Oxe2x80x2,Oxe2x80x2-tetraethyl S,Sxe2x80x2-methylenebis-(phosphorodithioate)], fosthiazate [N-(O-methyl-S-sec-butyl)phosphorylthiazolidin-2-one], etc.; carbamate compounds such as BPMC [2-sec-butylphenylmethylcarbamate], benfuracarb [ethyl N-(2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio]-N-isopropyl-xcex2-alaninate], propoxur [2-isopropoxyphenyl N-methylcarbamate], carbosulfan [2,3-dihydro-2,2-dimethyl-7-benzo[b]furanyl N-dibutylaminothio-N-methylcarbamate], carbaryl [1-naphthyl N-methylcarbamate], methomyl [S-methyl-N-[(methylcarbamoyl)oxy]thioacetoimidate], ethiofencarb [2-(ethylthiomethyl)phenylmethylcarbamate], aldicarb [2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime], oxamyl [N,N-dimethyl-2-methylcarbamoyloxyimino-2-(methylthio)acetamide], fenothiocarb [S-4-phenoxybutyl-N,N-dimethylthiocarbamate], etc.; pyrethroid compounds such as ethofenprox [2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzylether], fenvalerate [(RS)-xcex1-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate], esfenvalerate [(S)-xcex1-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)-3-methylbutyrate], fenpropathrin [(RS)-xcex1-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS)-xcex1-cyano-3-phenoxybenzyl (1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1RS, 3RS)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], cyhalothrin {(RS)-xcex1-cyano-3-phenoxybenzyl (Z)-(1RS, 3RS)-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S)-xcex1-cyano-m-phenoxybenzyl (1R,3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate], cycloprothrin [(RS)-xcex1-cyano-3-phenoxybenzyl (RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate], fluvalinate [xcex1-cyano-3-phenoxybenzyl N-(2-chloro-xcex1,xcex1,xcex1-trifluoro-p-tolyl)-D-valinate], bifenthrin [2-methylbiphenyl-3-ylmethyl (Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylpropanecarboxylate], acrinathrin [(1R-{1xcex1(S*),3xcex1(Z)}]-2,2-dimethyl-3-[3-oxo-3-(2,2,2-trifluoro-1-(trifluoromethyl)ethoxy-1-propenyl]cyclopropanecarboxlic acid cyano(3-phenoxyphenyl)methyl ester)], 2-methyl-2-(4-bromodifluoromethoxyphenyl)propyl(3-phenoxybenzyl) ether, tralomethrin [(S)-xcex1-cyano-3-phenoxybenzyl (1R)-cis-3-(1,2,2,2-tetrabromoethyl)-2,2-dimethylcyclopropanecarobxylate], silafluofen [[4-ethoxyphenyl(3-(4-fluoro-3-phenoxyphenyl)propyl)-dimethylsilane]], etc.; thiadiazine derivatives such as buprofezin [(2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-triadiazinan-4-one)], etc.; nitroimidazolidine derivatives; cartap [(S,Sxe2x80x2-(2-dimethylaminotrimethylene)-bis(thiocarbamate)], nereistoxin derivatives such as thiocyclam {N,N-dimethyl-1,2,3-trithian-5-ylamine], bensultap [S,Sxe2x80x2-2-dimethylaminotrimethylene di(benzenethiosulfonate)], etc.; N-cyanoamidine derivatives such as N-cyano-Nxe2x80x2-methyl-Nxe2x80x2-(6-chloro-3-pyridylmethyl)acetamidine, etc.; chlorinated hydrocarbon compounds such as endosulfan [6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathepinoxide], gamma-BHC [1,2,3,4,5,6-hexachlorocyclohexane], 1,1-bis(chlorophenyl)-2,2,2-trichloroethanol], etc.; benzoylphenylurea compounds such as chlorflazuron [1-(3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridin-2-yloxy)phenyl)-3-(2,6-difluorobenzoyl)urea], teflubenzuron [1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea], flufenoxuron [1-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)-3-(2,6-difluorobenzoyl)urea], etc.; formamidine derivatives such as amitraz [N,Nxe2x80x2-[(methylimino)dimethylidine] di-2,4-xylidine], chlordimeform [Nxe2x80x2-(4-chloro-2-methylphenyl)-N,N-dimethylmethanimidamide], etc.; thiourea derivatives such as diafenthiuron [N-(2,6-diisopropyl-4-phenoxyphenyl)-Nxe2x80x2-tert-butylcarbodiimide], etc.; phenylpyrazole compounds; tebufenozide [N-tert-butyl-Nxe2x80x2-(4-ethylbenzoly)-3,5-dimethylbenzohydrazide]; 4-bromo-2-(4-chlorophenyl)-1-ethoxymethyl-5-trifluoromethylpyrrol-3-carbonitrile; bromopropylate [isopropyl 4,4xe2x80x2-dibromobenzylate]; tetradifon [4-chlorophenyl 2,4,5-trichlorophenyl sulfone]; quinomethionate [S,S-6-methylquinoxalin-2,3-diyldithiocarbonate]; propargite [2-(4-tert-butylphenoxy)cyclohexylprop-2-yl sulfite]; fenbutatin oxide [bis[tris(2-methyl-2-phenylpropyl)tin]oxide]; hexythiazox [(4RS,5RS)-5-(4-chlorophenyl)-N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidin-3-carboxamide]; clofentezine [3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine]; pyridaben [2-tert-butyl-5-(4-tert-butylbenzylthio)-4-chloropyridazin-3(2H)-one]; fenpyroximate [tert-butyl (E)-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminoxymethyl]benzoate], tebufenpyrad [N-(4-tert-butylbenzyl)-4-chloro-3-ethyl-1-methyl-5-pyrrazolcarboxamide]; polynactin complex [tetranactin, dinactin, trinactin]; milbemectin; avermectin; ivermectin, azadirachtin [AZAD]; pyrimidifen [5-chloro-N-[2-{4-(2-ethoxyethyl)-2,3-dimethylphenoxy}-ethyl]-6-ethylpyrimidin-4-amine]; pymetrozine [2,3,4,5-tetrahydro-3-oxo-4-[(pyridin-3-yl)-methyleneamino]-6-methyl-1,2,4-triazine; and the like.
Examples of the plant diseases against which the compounds of the present invention exhibit controlling effects are as shown below.
rice plant: blast (Pyricularia oryzae), brown spot of rice plant (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani);
wheat, barley, etc.: powdery mildew (Erysiphe graminis), scab (Gibberella zeae), rust (Puccinia struiformis, P. graminis, P. recondita, P. hordei), snow blight (Typhula sp., Micronectriella nivalis), loose smut (Ustilago tritici, U. nuda), bunt (Tilletia caries), eye spot (Pseudocercosporella herpotrichoides), scald (Rhynchosporium secalis), specked leaf blotch (Septoria tritici), glume blotch (Leptosphaeria nodorum);
citrus: melanose (Diaporthe citri), scab (Elsinoe fawcetti), fruit rot (Penicillium digitatum, P. italicum);
apple: blossom blight (Sclerotinia mali), canker (Valsa mali), powdery mildew (Podosphaera leucotricha), Alernaria blotch (Alternaria mali), scab (Venturia inaequalis);
pear: scab (Venturia nashicola, V. pirina), black spot (Alernaria kikuchiana), rust (Gymnosporangium haraeanum);
peach: brown rot (Sclerotina cinerea), (Cladosporium carpophilum), Phomopsis rot (Phomopsis sp.);
grape: anthracnose (Elsinoe ampelina), ripe rot (Glomerella cingulata), powdery mildew (Uncinula necator) , rust (Phakopsora ampelopsidis), black rot (Guignardia bidwellii), downy mildew (Plasmopare viticola);
persimmon: anthracnoce (Gloeosporium kaki), leaf spot (Cercospora kaki, Mycosphaerella newae);
cucumber, melon, etc.: anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), gummy stem blight (Mycosphaerella melonis), Fusarium wilt (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), late blight (Phytophthora sp.), damping-off (Pythium sp.);
tomato: early blight (Alternaria solani), leaf mold (Cladosporium fulvum), late blight (Phytophthora infestans);
eggplant: brown spot (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum);
Cruciferae vegetable: Alternaria leaf spot (Alternaria japonica), white spot (Cercosporella brassicae);
Welsh onion: rust (Puccinia allii);
soybean: purple stain (Cercospora kikuchii), Sphaceloma scab (Elsinoe glycines), pod and stem blight (Diaporthe phaseolorum var. sojae);
kidney bean: anthracnose (Colletotrichum lindemthianum);
peanut: leaf spot (Cercospora personata), brown leaf spot (Cercospora arachidicola);
pea: powdery mildew (Erysiphe pisi);
potato: early blight (Alernaria solani), late blight (Phytophthora infestans);
strawberry: powdery mildew (Sphaerotheca humuli);
tea: net blister blight (Exobasidium reticulatum), white scab (Elsinoe leucospila);
tobacco: brown spot (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), late blight (Phytophthora nicotianae);
beet: Cercisoira leaf spot (Cercospora beticola);
rose: black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa);
chrysanthemum: leaf blight (Septoria chrysanthemi-indici), rust (Puccinia horiana);
various crops: gray mold (Botrytis cinerea), stem rot (Sclerotinia sclerotiorum); and the like.

Triazolone derivatives, use thereof, and intermediates therefor

Abstract: wherein R1 represents optionally substituted C1-10 alkyl, A1xe2x80x94L1xe2x80x94, A1xe2x80x94ONxe2x95x90CA2, etc.; R2 represents hydrogen, C1-6 alkyl, etc.; R3 represents C1-6 alkoxy, etc.; one of T, U, and V represents CR4, another represents CH or nitrogen, and the remaining one represents CR5 or nitrogen; and W represents CR6 or nitrogen.


The invention pertains to a high resolution imaging microscope, and more specifically, to a digital imaging spectrophotometer (DIS) configured to enable the direct determination of the ground state absorption spectra of microscopic samples from violet to near infrared. The instrument is capable of simultaneously recording hundreds of spectra, and can, using image processing techniques identify features (such as a single microbial cell) on a microscope slide or thin section. The invention additionally relates to the use of such an instrument.

Imaging spectroscopy is defined as the combined analysis of both spatial and spectral information so that each picture element (pixel) in a two dimensional scene includes a third dimension of spectral information. This means that the spectrum of any pixel or group of pixels within an image can be measured. Digital Imaging Spectrophotometers/Spectroscopy (DIS) combine imaging spectroscopy with digital image processing techniques. DIS is a powerful screening tool which can be considered functionally equivalent to tens of thousands of spectrophotometers operating in parallel. DIS was developed for the rapid and noninvasive analysis of bacterial mutants directly on petri dishes.
The ColonyImager, is a low cost, user-friendly, high performance digital imaging spectrophotometer which has been redesigned and brought to market by KAIROS Scientific (Santa Clara, Calif.). This instrument supports spectral acquisition in both transmission and reflectance mode. In addition, fluorescence emission images can be acquired by selection of an appropriate long-pass filter. In order to obtain radiometrically calibrated spectra, one must correct for the wavelength response of the detector and optics. This has been successfully accomplished so that the quality of spectra is as good or better than that obtained from a double beam spectrophotometer. With 5 nm bandpass and data taken at 5 nm intervals, the ColonyImager can easily detect 2.5 nm spectral shifts. This is close to the limit imposed by a diffraction grating; therefore, conventional spectrophotometers are not much better in spectral resolution.
The first workstation based imaging spectrophotometer for analysis of petri plates was sold in 1991 and the PC based ColonyImager was brought to market in 1993, which also marked the first international sale of this device. This instrument has recently been featured in two technical articles and three scientific reviews, including a product review in Nature and a chapter in Methods in Enzymology. KAIROS is the sole source for this state-of-the-art equipment.

High resolution imaging microscope (HIRIM) and uses thereof


A glitch filter is disclosed herein. The glitch filter includes a high glitch filter circuit, a low glitch filter and a control circuit. The high glitch filter circuit is configured for generating a pull-up control signal in accordance with the input signal. The low glitch filter circuit is configured for generating a pull-down control signal in accordance with the input signal. The control circuit is configured for determining the logic level of the output of the glitch filter in accordance with the pull-up control signal and the pull-down control signal. A filtering method for filtering glitches is disclosed herein as well.

1. Field of Invention
The present invention relates to the integrated circuits. More particularly, the present invention relates to a glitch filter.
2. Description of Related Art
Electronic circuits are subject to signal distortion and noise in operation. The signal distortion and the noise may significantly reduce the performance of the electronic circuits. In certain cases, the signal distortion and the noise may even cause the operation of the electronic circuits failed. For example, there exists a noise "glitch", which is often considered as an aperiodic noise in the operation of the electronic circuits.
FIG. 1A is a circuit diagram of a glitch filter 100 according to the prior art. As shown in FIG. 1A, the glitch filter 100 includes a high glitch filter 120 and a low glitch filter 140, and the high glitch filter 120 is connected to the low glitch filter 140 in series. At first, an input signal Vin is sent to one of the inputs of the NAND gate 122 directly and to another one of the inputs of the NAND gate 122 through a rising edge delay cell 124 which provides a delay time tdr on the rising edge of the input signal Vin, and the high glitch with pulse width less than the delay time tdr will be filtered. Second, the output of the high glitch filter is connected to the one of the inputs of the NOR gate 142 and to the another one of the inputs of the NOR gate 142 through a falling edge delay cell 144 which provides a delay time tdf on the falling edge of the input signal Vin. Thus, the low glitch with pulse width less than the delay time tdf will be filtered.
FIG. 1B is a wave diagram of the glitch filter 100 according to the prior art. As shown in FIG. 1B, if the input signal Vin oscillates during its enabling period (i.e., the time being logic "1"), the glitch filter 100 is expected to output a smooth signal with high logic level. However, in practical application, the glitch filter 100 filters the first high glitch and makes the low glitch wider than working range of the glitch filter 100, and the glitch filter toggles its output to low logic level for a while. In this case, the aforementioned low logic level is considered as a loophole, which refers to that the glitch filter 100 cannot correctly filter the input signal Vin. Further, as shown in the FIG. 1A, the glitch filter 100 may add more delay to the edges of the input signal Vin, which has some impact to the certain propagation delay sensitive circuit.
Therefore, a heretofore unaddressed need exists in the art to address the aforementioned deficiencies and inadequacies.