Popular You. Tube to MP3 Site Dies Under Crushing Weight of Record Company Litigation. The operators of You. Its actually remarkable that YouTubeMP3. org even survived this long. The websites sole purpose is enabling users to download audio tracks that they dont. The Federal Trade Commission, the US government body in charge of consumer protection and investigating anticompetitive marketplace practices, has announced that it. Tube MP3. org, a popular website for turning the audio tracks of You. Tube videos into MP3s, have agreed to shut down the site and hand over the domain to the RIAA. This predictable outcome comes after 1. California court. Poor little You. Tube MP3. Its actually remarkable that You. Tube MP3. org even survived this long. The websites sole purpose is enabling users to download audio tracks that they dont have permission to download. This practice is commonly known as stream ripping, and record companies have said that its bigger than piracy. In the case of, say, the latest Taylor Swift single which is awful by the way, You. Tube MP3. org lets you rip the song in a matter of seconds. No need to buy it on i. Tunes or, God forbid, at a record store. Everything is free on the internet. Until its not. While You. Tube MP3. org is hardly the only stream ripping service on the internet, it is one of the most popular. According to Alexa traffic statistics, You. Tube MP3. org has been in the top 4. This might be why record companies decided to take You. Tube MP3. org to court. And just to drive this point home You. Tube MP3. org never had a chance. Faced with the armies of lawyers that companies like Capitol Records, Sony Music, and Warner Brothers Records can employ, a simple little website like this one would be lucky to last a week. Its been almost year, however, since the consortium of record companies first sued You. Tube MP3. org. In the end, the parties decided on a settlement rather than letting a judge decide the websites fate. In addition to shutting down You. Tube MP3. org and handing over its domain, a proposed final judgement submitted Friday states the owners of the site will pay the record companies an undisclosed sum and refrain from knowingly designing, developing, offering, or operating any other infringing stream ripping service. For now, You. Tube MP3. That means users will have a few more hours or even days to download free music from You. Tube. And once You. Tube MP3. org goes away, theyll have to use another service until that one gets shut down by the record companies. The RIAA can play this game of whack a mole forever. After all, its been doing this since the Napster days. Why stop nowTorrent.
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What is Microsoft Access. This page hopes to explain to you What is Microsoft Access in simple terms. Microsoft Access has been around for some time, yet people often still ask me what is Microsoft Access and what does it do Microsoft Access is a part of the Microsoft Office Suite. It does not come with all versions of Microsoft Office, so if you specifically want Microsoft Access make sure the office suite you are purchasing has it. Microsoft Access has the look and feel of other Microsoft Office products, including its layout and navigational aspects. That is where the similarity ends. Microsoft Access is a database and, more specifically, a relational database. This will be explained in more detail later. Note This article doesnt apply to Access web apps the kind of database you design with Access and publish online. Access has an. mdb extension by default, whereas Microsoft Word has the. Although this has changed in Access 2. Early versions of Access cannot read accdb extensions but Microsoft Access 2. Access. The above is a bried overview of what is Microsoft Access. Now lets look at it in a bit more detail. What is Microsoft Access made up of The Microsoft Access Database is made up of 7 major components Tables Relationships Queries Forms Reports Macros Modules. The following gives a quick overview of each component. Tables. The tables are the backbone and the storage container of the data entered into the database. Delete Query Tutorial. The Delete query in MS Access SQL command used to remove one or more rows of data from a relational database table. The number of rows deleted. AfterInsert Event Access Visual Basic form event programming example. Download Microsoft Access Templates Northwind Sales Database Examples. This ms access database templates works on Microsoft Access 2013 and available for free as. If the tables are not set up correctly, with the correct relationships, then the database may be slow, give you the wrong results or not react the way you expect. So, take a bit of time when setting up your tables. Queries, forms, etc. The tables that contain data look a bit like a table in Microsoft Word or a Microsoft Excel Spreadsheet, when opened. They have columns and rows as does a table in Microsoft Word and an Excel worksheet. Each of the columns will have a field name at the top and each of the rows will represent a record. As an example Relationships. Relationships are the bonds you build between the tables. They join tables that have associated elements. To do this there is a field in each table, which is linked to each other, and have the same values. Queries. Are the means of manipulating the data to display in a form or a report. Queries can sort, calculate, group, filter, join tables, update data, delete data, etc. Their power is immense. The Microsoft Access database query language is SQL Structured Query Language. The need to know SQL is not required in the early stages of learning Access. Microsoft Access writes the SQL for you, after you tell it what you want, in the Design view of the queries window. Forms. Forms are the primary interface through which the users of the database enter data. The person who enters the data will interact with forms regularly. The programmer can set the forms to show only the data required. By using queries, properties, macros and VBA Visual Basic for Applications, the ability to add, edit and delete data can also be set. Forms can be set up and developed to reflect the use they will be required for. Reports. Reports are the results of the manipulation of the data you have entered into the database. Unlike forms, they cannot be edited. Reports are intended to be used to output data to another device or application, i. Microsoft Word or Microsoft Excel. Macros. Macros are an automatic way for Access to carry out a series of actions for the database. Access gives you a selection of actions that are carried out in the order you enter. Macros can open forms run queries, change values of a field, run other Macros, etc. Modules. Modules are the basis of the programming language that supports Microsoft Access, The module window is where you can write and store Visual Basic for Applications VBA. Advanced users of Microsoft Access tend to use VBA instead of Macros. If you would like to learn VBA, I have a simple step by step lessons. Click here to find out more. All of the above components are persistent this means that changes are saved when you move from one component to another, not when the database is closed, as in a Microsoft Word Document. I hope the above give you a bit of an idea of what is Microsoft Access and what it includes. Limitations. The total size of a database file. MDB is limited only by the storage capacity of your PC Microsoft quote the maximum database size of 2 Gigabyte 2. Megabytes. These figures are for pre 2. Microsoft Access. Very few realistic limitations exist, though here are some parameters Maximum table size. Gb. No. if fields in a record or table. No. of indexes in a table or a record. Ni. of fields in an index. No. of tables in a query. Maximum size of a form or report. Characters in a memo field. MDB size. 2 Gb. Max Integer. Concurrent Users. No. of characters in object names. What is Microsoft Access as compared to a Relational Database. Now that you understand a bit of what is Microsoft Access. The relational database was invented by E. F. Codd at IBM in 1. The power of a relational database is the ability to bring a lot of information together quickly. I am not going into too much technical detail of what a relational database but hope to explain it in simple terms, so it is possibly not 1. To me these are the rules of a relational database No duplicate data except linked fields explained shortlyInformation is broken into categories. Data is broken down to the smallest useable bit. For example a persons name would be broken down into 4 sperate sections title, first name, middle name and last name. Each record has a unique identifier, this distinguishes a particular record from any other record. To explain this I will give an example below For the purpose of this example, we will be looking at a Library data base from a relational database viewpoint. For a Library database we would want to collect the following information Information about the books Information about the borrowers Information about when a book was borrowed and by whom. You may be tempted to include all this information within the one table. Once you start entering data the following occurs Entering data this way requires multiple entries and duplicate data in some of the columns This can lead to the following problems Data entry errors see bolded items The user having to enter the same information over and over The database would grow very big, very quickly, causing it to run slower. Therefore, to meet the rules of a relational database we would first break this one large table into smaller tables of like information categories. As an example Table One tbl. Book would contain information about the books Table Two tbl. Borrower would contain information about the borrowers and. Table Three tbl. Loan would contain information about the borrowing of a book. The next step is to list all the facts you think are required for each of these tables underneath them. I have included the examples below for each of the tables for the library database. The primary key and foreign key fields will be explained a bit later. Note The fields have been broken down in to their smallest logical part. As an example, a persons name has been broken down to Surname First name Title. The information is only recorded once, i. Loan table. Primary Key Unique Identifier. An important part of determining the fields for each table is deciding which field if any is suitable as the primary key. The power of a relational database is the ability to bring a lot of information together quickly. For this to work efficiently and effectively, Microsoft Access needs to be able to identify unique records. For this reason, one field or a set of fields needs to be unique. This can be a unique identification number such as a Medicare number, Employee ID number, Pension number, etc. A primary key cannot contain duplicate values, e. A primary key cannot contain null values, therefore a field such as a phone number is not suitable, as you may not know the persons phone number when you first enter them into the database Also, if the information contained in the Primary Key is likely to be altered, then it is best to avoid this field as well. If a unique identifier cannot be identified which is more than likely, you can add a field, which will automatically increase sequentially by one, thus providing the record with a unique identifier. Foreign Keys. The Foreign Key is the field that links a related table to the main table. As an example, in the library database, a borrower may appear many times in the Loan table, as a borrower may borrow many books. 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Glossary of Technical Film and Broadcasting Terms.Glossary of Technical Film and Broadcasting Terms.ITU Standards. ITU6.The standard for analog PAL 6.Equivalent to the NTSC 5.SMPTE ST 1. 70 standard.ITU R BT4. 70. An international standard for the PALcomposite analog television system.ITU R6. 01. An international standard for component digital television from which was derived SMPTE ST 1.The best free and paid streaming software for PC Telestream Wirecast recommended Wirecast is a video streaming software and a switcher from Telestream.EBU 3. 24. 6 E standards.ITU R6. 01 defines the sampling systems, matrix values and filter characteristics for both Y, B Y, R Y and RGB component digital television signals.This document was formerly known as CCIR 6.Rec 6. 01. 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The SMPTE standard for the serial digital interface for standard definition 1.Fsc composite interfaces.Often referred to as SDISMPTE ST 2.The SMPTE standard for embedding AES audio into standard definition serial digital interfaces.SMPTE ST 2. 74. The SMPTE standard for HDTV 1.SMPTE ST 2. 76. The SMPTE standard for transmission of AES digital audio over coaxial cable.SMPTE ST 2. 91. The SMPTE standard for Ancillary Data Packet and Space Formatting.SMPTE ST 2. 92. The SMPTE standard for the 1.Gbs serial digital interface for High Definition television signals.Often referred to as HD SDISMPTE ST 2.Television 7. 20 x 4.Active Line at 5.Hz Progressive Scan Production Digital Representation.SMPTE ST 2. 96. The SMPTE standard for HDTV 1.SMPTE ST 2. 99. The SMPTE standard for embedding AES audio into high definition serial digital interfaces.SMPTE ST 3. 05. Television Serial Data Transport Interface SDTISMPTE ST 3.The SMPTE standard for the encoding Date and Time Zone information into SMPTE ST 1.Time code signals.SMPTE ST 3. 10. Television Synchronous Serial Interface for MPEG 2 Digital Transport Streams.SMPTE ST 3. 49. Television Transport of Alternate Source Image Formats through SMPTE ST 2.SMPTE ST 3. 72. The SMPTE standard for the dual link 1.Gbs serial digital interface for High Definition television signals.SMPTE ST 4. 24. The SMPTE standard for the nominal 3.Gbs serial digital interface for High Definition television signals.RP 1. 68. The SMPTE Recommended Practice for the definition of the vertical interval switching point for synchronous video switching.This recommended practice also defines a default alignment between standard definition and high definition synchronizing pulse signals.Other Standards. AES3 1.A digital audio standard defined in 1.AESEBUAES3 2. 00.A digital audio standard defined and updated in 2.AESEBUDVB ASIDigital Video Broadcast Asynchronous Serial Interface.A standard definition digital video standard with a bit rate of 2.Mbs. EBU TECH 3. EThe EBU recommendation for the parallel interface of 6.This is a revision of the earlier EBU Tech 3.E standard, which was in turn derived from ITU R6.EIA 6. 08. A Closed Caption standard for SD SDI television signals.EIA 7. 08. A Closed Caption standard for HD SDI television signals.M2. SA digital video standard similar to DVB ASI but using a different method to time incoming data packets.This limits the bit rate of M2.S to 1. 00. Mbs. RS 2.A common interface standard for serial data communications equipment.RS 4. 22. A serial data standard which allows one transmitter to send communication data to up to 1.RS 4. 85. A party line serial data standard with up to 3.Only one line transmitts data at a time while all other lines can receive simultaneously.Terms. 10. 80p2. A progressively scanned high definition video format with 1.F4 2 2. A commonly used term for a component digital video format.The details of the format are specified in the ITU R6.The numerals 4 2 2 denote the ratio of the sampling frequencies of the luminance channel to the two colour difference channels.For every four luminance samples, there are two samples of each colour difference channel.A commonly used term for a high resolution component digital video format.The numerals 4 4 4 denote the ratio of the sampling frequencies of the luminance channel to the two colour difference channels.For every four luminance samples, there are four samples of each colour difference channel.RGB format with equal sampling rates for each of the colour channels.These signals are commonly carried on a pair of coax cables according to the SMPTE ST 3.Fsc. A commonly used term for a composite digital video format.The details of the format are specified in the ITU R6.The numerals 4. Fsc denote that the sampling frequency is 4 times the colour subcarrier frequency approximately 1.MHz for NTSC and 1.MHz for PALAaton.Code. An in camera film timecode system, exposed in the camera during filming, carries data which is both machine readable a matrix of dots for each film frame and man readable for its conversion into SMPTE time code.Aaton. Code specifically contains the production timecode synchronizing data, hour, minute, second, frame, year, month, day, production ID, camera ID and camera speed. Install Vmware Tools Red Hat 6 Logo . Aaton. 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A device which takes embedded data from the video bit stream and translates it into human readable text.This text is then burnt into the on screen picture in character windows.This is usually time code data, scene, take and other post production data.Alpha channel. In electronic production and post production, there is increasing application of 4 4 4 4 encoding which provides full bandwidth R, G, and B plus the additional alpha channel to carry processing information.An adaptation from computer graphics, the alpha channel may contain information for linear key, for luminance andor chroma transparency, for variable edge enhancement, and similar image processing information.Analog. 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Worldwide 1.March 3. 1, 2. 01.Media. Operating system.SIA Elsana astopadsmit gadu laik uzkrt pieredze un zinanas, k ar augsti kvalificti darbinieki sniedz iespju realizt klientu vlmes preczi un.Theres a second use for Freedom, a simple app that lets you block distracting sites like Twitter for a few minutes, hours, or days.As the apps blog points out.Noregistration upload of files up to 250MB.Not available in some countries.Wii system software.CPU7. 29 MHz IBMPower.PC Broadway 1. Memory.MB total, 2. MB Mo.Sys 1. T SRAM, 3.MHz, 2. 7. GBs bandwidth.Storage. 51. 2 MB Internal flash memory.FO2/VWAZ/F1L8VZ7F/FO2VWAZF1L8VZ7F.MEDIUM.jpg' alt='Installer Pokemon Ti 83 Plus' title='Installer Pokemon Ti 83 Plus' />Removable storage.SDSDHC card. Game.Cube Memory Card.Display. Graphics.MHz ATIHollywood1.Controller input.Wii Remote Plus, Wii Balance Board, Nintendo Game.Cube controller, Nintendo DS1.Connectivity. Wi Fi.IEEE 8. 02. 1. 1bg.Bluetooth. 2 USB 2.LAN Adapter via USBOnline services.Nintendo Wi Fi Connectionclosed May 2.Wii. Connect. 24closed June 2.Wii Shop Channel.Best selling game.Wii Sportspack in, except in Japan and South Korea 8.March 3. 1, 2. 01.Mario Kart Wii, 3.March 3. 1, 2. 01.Backwardcompatibility.Game. Cubefirst model onlyPredecessor.Game. Cube. Successor.Wii UThe Wii WEE is a home video game console released by Nintendo on November 1.As a seventh generation console, the Wii competed with Microsofts Xbox 3.Sonys Play. Station 3.Nintendo states that its console targets a broader demographic than that of the two others.As of the first quarter of 2.Wii leads its generation over Play.Station 3 and Xbox 3.December 2. 00. 9, the console broke the sales record for a single month in the United States.The Wii introduced the Wii Remotecontroller, which can be used as a handheld pointing device and which detects movement in three dimensions.Another notable feature of the console is the now defunct Wii.Connect. 24, which enabled it to receive messages and updates over the Internet while in standby mode.Like other seventh generation consoles, it features a game download service, called Virtual Console, which features emulated games from past systems.It succeeded the Game.Cube, and early models are fully backward compatible with all Game.Cube games and most accessories.Nintendo first spoke of the console at the E3 2.E3 2. 00. 5. Nintendo CEO Satoru Iwata revealed a prototype of the controller at the September 2.Tokyo Game Show. 2.At E3 2. 00. 6, the console won the first of several awards.By December 8, 2.In late 2. 01. 1, Nintendo released a reconfigured model, the Wii Family Edition, which lacks Nintendo Game.Cube compatibility this model was not released in Japan.The Wii Mini, Nintendos first major console redesign since the compact SNES, succeeded the standard Wii model and was released first in Canada on December 7, 2.The Wii Mini can only play Wii optical discs, as it omits Game.Cube compatibility and all networking capabilities this model was not released in Japan, Australia, or New Zealand.The Wiis successor, the Wii U, was released on November 1. Ms Office Accounting Professional 2009 Keygen Crack . On October 2. 0, 2.Nintendo confirmed it had discontinued production of the Wii in Japan and Europe, although the Wii Mini is still in production and available in Europe.History. The console was conceived in 2.Nintendo Game. Cube was first released.According to an interview with Nintendo game designer Shigeru Miyamoto, the concept involved focusing on a new form of player interaction.The consensus was that power isnt everything for a console.Too many powerful consoles cant coexist.Its like having only ferocious dinosaurs.They might fight and hasten their own extinction.In 2. 00. 3, game engineers and designers were brought together to develop the concept further.By 2. 00. 5 the controller interface had taken form, but a public showing at that years Electronic Entertainment Expo E3 was canceled.Miyamoto stated that the company had some troubleshooting to do.So we decided not to reveal the controller and instead we displayed just the console.Nintendo president Satoru Iwata later unveiled and demonstrated the Wii Remote at the September Tokyo Game Show.The Nintendo DS is said to have influenced the Wiis design.Designer Kenichiro Ashida noted, We had the DS on our minds as we worked on the Wii.We thought about copying the DSs touch panel interface and even came up with a prototype.The idea was eventually rejected because of the notion that the two gaming systems would be identical.Miyamoto also stated,.DS had flopped, we might have taken the Wii back to the drawing board.In June 2. 01. 1 Nintendo unveiled the prototype of its successor to the Wii, to be known as Wii U.Name. The console was known by the code name Revolution until April 2.E3. 3. 0Nintendos spelling of Wii with two lower case i characters is intended to resemble two people standing side by side representing players gathering together and to represent the Wii Remote and Nunchuk.One reason the company has given for this name choice since the announcement is Wii sounds like we, which emphasizes that the console is for everyone.Wii can easily be remembered by people around the world, no matter what language they speak.No confusion. 3. 1Some video game developers and members of the press stated that they preferred Revolution over Wii.Forbes expressed a fear that the name would convey a continued sense of kidiness to the console.The BBC reported the day after the name was announced that a long list of puerile jokes, based on the name, had appeared on the Internet.Nintendo of Americas Vice President of Corporate Affairs Perrin Kaplan defended the choice of Wii over Revolution and responded to critics of the name, stating Live with it, sleep with it, eat with it, move along with it and hopefully theyll arrive at the same place.Nintendo of Americas president Reggie Fils Aime acknowledged the initial reaction and further explained the change Revolution as a name is not ideal its long, and in some cultures, its hard to pronounce.So we wanted something that was short, to the point, easy to pronounce, and distinctive.Thats how Wii, as a console name, was created.Nintendo has stated that the official plural form is Wii systems or Wii consoles.The Nintendo Style Guide refers to the console as simply Wii, not Nintendo Wii,3.Nintendo has marketed outside Japan without the company name in its trademark.Launch. On September 1.Nintendo announced release information for Japan, North and South America, Oceania, Asia and Europe including dates, prices, and projected unit distribution figures.It was announced that the majority of the 2.Americas, and 3. 3 titles would be available at its launch.The Wii was launched in the United States on November 1.United Kingdom on December 8, 2.The United Kingdom experienced a widespread shortage of Wii units in many High Street and online stores, and was unable to fulfill all pre orders at its release.The Wii was launched in South Korea on April 2.Taiwan on July 1.Software library.Retail copies of games are supplied on proprietary, DVD type Wii optical discs, which are packaged in keep cases with instructions.In Europe, the boxes have a triangle at the bottom corner of the paper sleeve insert side.The triangle is color coded to identify the region for which the title is intended and which manual languages are included.The console supports regional lockout software purchased in a region can be only played on that regions hardware.New games in Nintendos flagship franchises including The Legend of Zelda, Super Mario, Pokmon, and Metroid have been released, in addition to many original titles and third party developed games.Nintendo has received third party support from companies such as Ubisoft, Sega, Square Enix, Activision Blizzard, Electronic Arts and Capcom, with more games being developed for Wii than for the Play.Station 3 or Xbox 3.Nintendo also launched the New Play Control Game.Cube games for the Wii featuring updated controls.The Virtual Console service allows Wii owners to play games originally released for the Nintendo Entertainment System, Super Nintendo Entertainment System, Nintendo 6.Segas GenesisMega Drive and Sega Mark IIISega Master System,4.NECs Turbo. Grafx 1. How to Flash a Black. Berry. These days many people own high tech smart phones such as the Black. Berry. Since these phones are akin to mini computers, the running system, program files and menu applications need to be maintained. One of the ways to maintain your Black. Berry and make sure it runs smoothly with its service provider is to perform a flash on the device. This will ensure that all the latest software is installed and all bugs are removed. JupiterimagesPhotos. Getty Images. Step. Plug your Black. Berry into your computer via the USB port and open the Black. Berry Desktop Manager program. If you do not have Black. Berry Desktop Manager installed, you need to insert the program disc that came with your Black. Berry when you purchased it. Follow the prompts to install it. Step. Click on the Device Manager tab in program window and find which com port on your computer your Black. Berry is installed on. 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Highlight and select it. Click OK when prompted to confirm. Flash Plugin UpdateStep. Click on the Roam tab at the top of the QPST screen, then click the Browse tab. Select your current Black. Berry service provider from the list of options and then click the Write To Phone tab at the bottom of the window. Your Black. Berry will now be flashed. Blackberry 8900 Free Download Adobe Flash Player,free Blackberry 8900 Free Download Adobe Flash Player download. Blackberry flash player, Adobe Flash Player 11. 3 beta 2. blackberry 8520 curve applications free download blackberry 8900 unlock calculator. Black. Berry Support Community Forums. The Black. Berry Device Support Community Forums have closed as of April 1, 2. Black. Berry remains committed to providing excellent customer support to our customers. We are delighted to direct you to the Crack. Berry Forums, a well established and thorough support channel, for continued Black. Berry device support. You can also continue to make use of official support options available for your Black. Berry smartphone. Black. Berry Contact Us Black. enspenspPlease be advised the BlackBerry Support Community Device Forums have closed and the BlackBerry Developer Support Forums have. Free tlcharger adobe flash player gratuit download software at UpdateStar Adobe Flash Player Plugin enables the display of multimedia and interactive. Berry Knowledge Base When we launched Crack. Berry. com 1. 0 years ago, we set out to make it a fun and useful destination where Black. Berry Smartphone owners could share their excitement and learn to unleash the full potential of their Black. Berry. A decade later, the Crack. Berry community is as active and passionate as ever and I know our knowledgeable members and volunteers will be excited to welcome and assist more Black. Berry owners with their questions. Kevin Michaluk, Founder, Crack. Enable Flash Player In Windows 10 Alkyne Wikipedia. A 3. D model of ethyne acetylene, the simplest alkyne. In organic chemistry, an alkyne is an unsaturatedhydrocarbon containing at least one carboncarbon triple bond. 1 The simplest acyclic alkynes with only one triple bond and no other functional groups form a homologous series with the general chemical formula Cn. H2n2. Alkynes are traditionally known as acetylenes, although the name acetylene also refers specifically to C2. H2, known formally as ethyne using IUPAC nomenclature. Like other hydrocarbons, alkynes are generally hydrophobic but tend to be more reactive. Subject content for GCSE Chemistry. C1. 3 Metals and their uses. Metals are very useful in our everyday lives. Ores are naturally occurring rocks that provide an. It is very difficult to find or develop a single material to meet all of the above criteria. In general, the binder formulations consist of at least two components a. Structure classification. Saturated hydrocarbons are hydrocarbons having only single covalent bonds between their carbons. They can be linear general formula C. Chemical propertieseditAlkynes are characteristically more unsaturated than alkenes. Thus they add two equivalents of bromine whereas an alkene adds only one equivalent in the reaction. Other reactions are listed below. In some reactions, alkynes are less reactive than alkenes. For example, in a molecule with an ene and an yne group, addition occurs preferentially at the ene. 2 Possible explanations involve the two bonds in the alkyne delocalising, which would reduce the energy of the systemcitation needed or the stability of the intermediates during the reaction. They show greater tendency to polymerize or oligomerize than alkenes do. The resulting polymers, called polyacetylenes which do not contain alkyne units are conjugated and can exhibit semiconducting properties. Structure and bondingeditIn acetylene, the HCC bond angles are 1. By virtue of this bond angle, alkynes are rod like. Correspondingly, cyclic alkynes are rare. Benzyne is highly unstable. The CC bond distance of 1. CC distance in alkenes 1. CC bond in alkanes 1. Illustrative alkynes a, acetylene, b, two depictions of propyne, c, 1 butyne, d, 2 butyne, e, the naturally occurring 1 phenylhepta 1,3,5 triyne, and f, the strained cycloheptyne. Triple bonds are highlighted blue. The triple bond is very strong with a bond strength of 8. Jmol. The sigma bond contributes 3. Jmol, the first pi bond contributes 2. Jmol and the second pi bond of 2. Jmol bond strength. Bonding usually discussed in the context of molecular orbital theory, which recognizes the triple bond as arising from overlap of s and p orbitals. In the language of valence bond theory, the carbon atoms in an alkyne bond are sp hybridized they each have two unhybridized p orbitals and two sp hybrid orbitals. Overlap of an sp orbital from each atom forms one spsp sigma bond. Each p orbital on one atom overlaps one on the other atom, forming two pi bonds, giving a total of three bonds. The remaining sp orbital on each atom can form a sigma bond to another atom, for example to hydrogen atoms in the parent acetylene. The two sp orbitals project on opposite sides of the carbon atom. Terminal and internal alkyneseditInternal alkynes feature carbon substituents on each acetylenic carbon. Symmetrical examples include diphenylacetylene and 3 hexyne. Terminal alkynes have the formula RC2. H. An example is methylacetylene propyne using IUPAC nomenclature. Terminal alkynes, like acetylene itself, are mildly acidic, with p. Ka values of around 2. They are far more acidic than alkenes and alkanes, which have p. Ka values of around 4. The acidic hydrogen on terminal alkynes can be replaced by a variety of groups resulting in halo, silyl, and alkoxoalkynes. The carbanions generated by deprotonation of terminal alkynes are called acetylides. 3Naming alkyneseditIn systematic chemical nomenclature, alkynes are named with the Greek prefix system without any additional letters. Examples include ethyne or octyne. In parent chains with four or more carbons, it is necessary to say where the triple bond is located. For octyne, one can either write 3 octyne or oct 3 yne when the bond starts at the third carbon. The lowest number possible is given to the triple bond. When no superior functional groups are present, the parent chain must include the triple bond even if it is not the longest possible carbon chain in the molecule. Ethyne is commonly called by its trivial name acetylene. In chemistry, the suffix yne is used to denote the presence of a triple bond. In organic chemistry, the suffix often follows IUPAC nomenclature. However, inorganic compounds featuring unsaturation in the form of triple bonds may be denoted by substitutive nomenclature with the same methods used with alkynes i. The position of unsaturation is indicated by a numerical locant immediately preceding the yne suffix, or locants in the case of multiple triple bonds. Locants are chosen so that the numbers are low as possible. Sometimes a number between hyphens is inserted before it to state which atoms the triple bond is between. This suffix arose as a collapsed form of the end of the word acetylene. The final e disappears if it is followed by another suffix that starts with a vowel. 4SynthesiseditCommercially, the dominant alkyne is acetylene itself, which is used as a fuel and a precursor to other compounds, e. Hundreds of millions of kilograms are produced annually by partial oxidation of natural gas 52 CH4 32 O2 HCCH 3 H2. OPropyne, also industrially useful, is also prepared by thermal cracking of hydrocarbons. Most other industrially useful alkyne derivatives are prepared from acetylene, e. Specialty alkynes are prepared by dehydrohalogenation of vicinal alkyl dihalides or vinyl halides. 6 Metal acetylides can be coupled with primary alkyl halides. Via the FritschButtenbergWiechell rearrangement, alkynes are prepared from vinyl bromides. Alkynes can be prepared from aldehydes using the CoreyFuchs reaction and from aldehydes or ketones by the SeyferthGilbert homologation. In the alkyne zipper reaction, alkynes are generated from other alkynes by treatment with a strong base. ReactionseditFeaturing a reactive functional group, alkynes participate in many organic reactions. Addition of hydrogen, halogens, and related reagentseditAlkynes characteristically undergo reactions that show that they are doubly unsaturated, meaning that each alkyne unit is capable of adding two equivalents of H2, halogens or related HX reagents X halide, pseudohalide, etc. Depending on catalysts and conditions, alkynes add one or two equivalents of hydrogen. Partial hydrogenation, stopping after the addition of only one equivalent to give the alkene, is usually more desirable since alkanes are less useful RCCR H2 cis RCHCRHThe largest scale application of this technology is the conversion of acetylene to ethylene in refineries. The steam cracking of alkanes yields a few percent acetylene, which is selectively hydrogenated in the presence of a palladiumsilver catalyst. For more complex alkynes, the Lindlar catalyst is widely recommended to avoid formation of the alkane, for example in the conversion of phenylacetylene to styrene. 7Similarly, halogenation of alkynes gives the vinyl dihalides or alkyl tetrahalides RCCR 2 Br. RCBr. 2CRBr. 2The addition of nonpolar EH bonds across CC is general for silanes, boranes, and related hydrides. The hydroboration of alkynes gives vinylic boranes which oxidize to the corresponding aldehyde or ketone. In the thiol yne reaction the substrate is a thiol. Acid promoted addition reactions are likewise analogous to those of alkenes, including Markovnikov selectivity. Hydrohalogenation gives the corresponding vinyl halides or alkyl dihalides, again depending on the number of equivalents of HX added. The hydration reaction gives an enol via the addition of one equivalent of water, a structure that tautomerizes to form a ketone or aldehyde. For example, the hydration of phenylacetylene gives acetophenone,8 and the Ph. PAu. CH3 catalyzed hydration of 1,8 nonadiyne to 2,8 nonanedione 9Ph. CCH H2. O Ph. COCH3. HCCC6. H1. CCH 2. H2. O CH3. COC6. H1. 2COCH3. Cycloadditions and oxidationeditAlkynes undergo diverse cycloaddition reactions. Most notable is the DielsAlder reaction with 1,3 dienes to give 1,4 cyclohexadienes. This general reaction has been extensively developed and electrophilic alkynes are especially effective dienophiles. The cycloadduct derived from the addition of alkynes to 2 pyrone eliminates carbon dioxide to give the aromatic compound. Other specialized cycloadditions include multicomponent reactions such as alkyne trimerisation to give aromatic compounds and the 221 cycloaddition of an alkyne, alkene and carbon monoxide in the PausonKhand reaction. |
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