An allyl group is a substituent with the structural formula H2C=CH−CH2R, where R is the rest of the molecule. It consists of a methylene bridge attached to a vinyl group; the name is derived from the Latin word for Allium sativum. In 1844, Theodor Wertheim isolated an allyl derivative from garlic oil and named it "Schwefelallyl"; the term allyl applies to many compounds related to H2C=CH−CH2, some of which are of practical or of everyday importance, for example, allyl chloride. A site adjacent to the unsaturated carbon atom is called allylic site. A group attached at this site is sometimes described as allylic. Thus, CH2=CHCH2OH "has an allylic hydroxyl group". Allylic C−H bonds are about 15% weaker than the C−H bonds in ordinary sp3 carbon centers and are thus more reactive; this heightened reactivity has many practical consequences. The industrial production of acrylonitrile by ammoxidation of propene exploits the easy oxidation of the allylic C−H centers: 2CH3−CH=CH2 + 2NH3 + 3O2 → 2CH2=CH−C≡N + 6H2OUnsaturated fats spoil by rancidification involving attack at allylic C−H centers.
Benzylic and allylic are related in terms of structure, bond strength, reactivity. Other reactions that tend to occur with allylic compounds are allylic oxidations, ene reactions, the Tsuji–Trost reaction. Benzylic groups are related to allyl groups. A CH2 group connected to two vinyl groups is said to be doubly allylic; the bond dissociation energy of C−H bonds on a doubly allylic centre is about 10% less than the bond dissociation energy of a C−H bond, allylic. The weakened C−H bonds reflect the high stability of the resulting pentadienyl radicals. Compounds containing the C=C−CH2−C=C linkages, e.g. linoleic acid derivatives, are prone to autoxidation, which can lead to polymerization or form semisolids. This reactivity pattern is fundamental to the film-forming behavior of the "drying oils", which are components of oil paints and varnishes; the term homoallylic refers to the position on a carbon skeleton next to an allylic position. In but-3-enyl chloride CH2=CHCH2CH2Cl, the chloride is homoallylic because it is bonded to the homoallylic site.
The allyl group is encountered in organic chemistry. Allylic radicals and cations are discussed as intermediates in reactions. All feature three contiguous sp²-hybridized carbon centers and all derive stability from resonance; each species can be presented by two resonance structures with the charge or unpaired electron distributed at both 1,3 positions. In terms of MO theory, the MO diagram has three molecular orbitals: the first one bonding, the second one non-bonding and the higher energy orbital is antibonding. Allylation is any chemical reaction. Allylation refers to the addition of an allyl anion equivalent to an organic electrophile: Carbonyl allylation is a type of organic reaction in which an activated allyl group is added to carbonyl group producing an allylic tertiary alcohol. A typical allylation of an aldehyde is represented by the following two-step process that begins with allylation followed by hydrolysis of the intermediate: RCHO + CH2=CHCH2M → CH2=CHCH2RCH CH2=CHCH2RCH + H2O → CH2=CHCH2RCH + MOHA popular reagent for asymmetric allylation is the "Brown reagent", allyldiisopinocampheylborane.
The introduction of allylic groups into molecular frameworks generates many opportunities for downstream diversification. A common method to introduce allyl moieties into organic molecules is through 1,2-allylation of carbonyl groups; the homoallylic alcohol products can undergo a variety of diversity-generating reactions such as ozonolysis and olefin metathesis. Allylmetal reagents such as allylboranes and allylindium compounds are used by organic chemists to introduce allyl groups. Allylstannanes are stable reagents in the allylmetal family, have been employed in a variety of complex organic syntheses. In fact, allylstannane addition is one of the most common methods for producing polypropionates and other oxygenated molecules with a contiguous arrays of stereocenters. Ley and coworkers used an allylstannane to allylate a threose-derived aldehyde en route to the macrolide antascomicin B, which structurally resembles FK506 and rapamycin, is a potent binder of FKBP12. Allylboration is often used to add allyl groups in a 1,2 fashion to aldehydes and ketones.
Thanks to decades of research, there is now a wide variety of organoboron reagents available to the synthetic chemist, including organoboranes that predictably yield products in high diastereo- and enantioselectivity. If a one-pot metal insertion and allylation procedure is required, indium- mediated allylation is an attractive option for generating homoallylic alcohols directly from allyl halides and carbonyl compounds. In general, the method is called the Barbier reaction, can employ a variety of metals such as magnesium, zinc and tin; the reaction is used as a milder form of the Grignard addition reaction, can tolerate aqueous solvents Organotantalum reagents are useful for conjugate addition to enones. Of particular interest is the ability of certain organotantalum reagents to promote the conjugate allylation of enones. Although the direct allylation of carbonyl groups is prevalent throughout the literature, little has been reported on the conjugate allylation of enones. Prior to Shibata and Baba's report, only three methods existed to selectively allylate enones, via: Hosomi Sakurai reaction, allylbarium reagents, allylcopper reagents.
Transmetalation of allyltin, alkynyltin, α-stannyl esters, allenyltin compounds with TaCl5 a
See also: Computer-aided design Computer-aided architectural design software programs are the repository of accurate and comprehensive records of buildings and are used by architects and architectural companies. The first program was installed back in the 1960s, to help architects save time instead of drawing their blueprints. Computer-aided design known as CAD was the type of program that architects used, but since CAD could not offer all the tools that architects needed to complete a project, CAAD developed as a distinct class of software. All CAD and CAAD systems employ a database with other properties of objects; the main distinction which causes one to speak of CAAD rather than CAD lies in the domain knowledge embedded in the system. A CAAD system differs from other CAD systems in two respects: It has an explicit object database of building parts and construction knowledge, it explicitly supports the creation of architectural objects. In a more general sense, CAAD refers to the use of any computational technique in the field of architectural design other than by means of architecture-specific software.
For example, software, developed for the computer animation industry, is used in architectural design. These programs can produce photo realistic 3d animations. Nowadays real-time rendering is being popular thanks to the developments in graphic cards; the exact distinction of what properly belongs to CAAD is not always clear. Specialized software, for example for calculating structures by means of the finite element method, is used in architectural design and in that sense may fall under CAAD. On the other hand, such software is used to create new designs. In 1974 Caad was a common topic of commercial modernization. CAAD has two types of structures in its program; the first system is surface structure which provides a graphics medium to represent three-dimensional objects using two-dimensional representations. Algorithms that allow the generation of patterns and their analysis using programmed criteria, data banks that store information about the problem at hand and the standards and regulations that applies to it.
The second system is deep structure which means that the operations performed by the computer have natural limitations. Computer hardware and machine languages that are supported by these make it easy to perform arithmetical operations and accurately. An illogical number of layers of symbolic processing can be built enabling the functionalities that are found at the surface. Another advantage to CAAD is the two way mapping of functionalities. NOS; the two instances of mapping are indicated to be between the surface structures and the deep structures. These mappings are abstractions that are introduced in order to discuss the process of design and deployment of CAAD systems. In designing the systems the system developers consider TM1. Here a one-to-one mapping is the typical statement, to develop a computer based functionality that maps as as possible into a corresponding manual design activity, for example, drafting of stairs, checking spatial conflict between building systems, generating perspectives from orthogonal views.
The architectural design processes tend to integrate models isolated so far. Many different kinds of expert knowledge, visualization techniques, media are to be combined; the design process covers the complete life cycle of the building. The areas that are covered are construction, reorganization, as well as destruction. Considering the shared use of digital design tools and the exchange of information and knowledge between designers and across different projects, we speak of a design continuum. An architect's work involves visually represented data. Problems are outlined and dealt with in a graphical approach. Only this form of expression serves as a basis for discussion. Therefore, the designer should have maximum visual control over the processes taking place within the design continuum. Further questions occur about navigation, associative information access and communication within large data sets. Architectural geometry Artificial Architecture Association for Computer Aided Architectural Design Research in Asia Comparison of CAD software Design computing Digital morphogenesis Geometric modeling kernel Kalay, Y..
Architecture's New Media. MIT Press, Massachusetts. Mark, E. Martens, B. & Oxman, R.. Preliminary stages of CAAD education. Automation in Construction, 12, 661-670. Maver, T.. Computer aided architectural design futures. Information and Software Technology, 35, 700-701. McGraw-Hill Inc.. Can Architecture Be Computerized? Engineering News Record, Vol. 223, No. 4. Ryan, R. L.. Computer Aided Architectural Graphics. Marcel Dekker, Inc. Szalapaj, P.. CAD Principles for Architectural Design. Architectural Press, Oxford. Several organisations are active in education and research in CAAD: Homepage ACADIA: Association for Computer Aided Design in Architecture. Homepage ASCAAD: Arab Society for Computer Aided Architectural Design Homepage CAAD Futures: Computer Aided Architectural Design futures foundation. Homepage CAADRIA: Association for Computer Aided Architectural Design Research in Asia Homepage eCAADe: Association for Education and Research in Computer Aided Architectural Desi
Fixer Upper is an American reality television series about home design and renovation aired on HGTV. The series stars Chip Gaines and Joanna Gaines, a married couple who own a home renovation and redecoration business in Waco, Texas; the show's pilot aired in May 2013, with the first full season beginning in April 2014, season two began in January 2015, season three began in December 2015, season four began in November 2016. The fifth and final season premiered on November 21, 2017. Fixer Upper became popular soon after its debut, the series is credited with the rise in popularity of "Farmhouse-chic" interior design in the late 2010s. In 2018, Zillow reported that homes with architectural features mentioned on the show, such as wainscoting, clawfoot bathtubs, barn doors, sold at an average of 30 percent above expected value. In addition, the show has generated an increase in tourism and economic development in Waco, where the show was filmed. Fixer Upper is produced by High Noon Entertainment producers Scott Feeley and Jim Berger, producers of the cooking show Cake Boss.
Prior to Fixer Upper and Joanna Gaines worked with clients on buying and remodeling homes. In total, the couple had worked on over 100 homes. On the show and Chip start by showing one couple three potential homes for purchase in central Texas, each of which requires a varying amount of repair or renovation. Once the couple chooses their home, Joanna designs; the buyers have an overall budget of under $200,000 with at least $30,000 in renovations. In March 2017, it was announced that Chip and Joanna Gaines would be getting a Fixer Upper spin-off series entitled Fixer Upper: Behind the Design; the half-hour show showcases. The show premiered on April 10, 2018; as of November 1, 2017 Joanna has teamed with Target Corporation to offer her Hearth & Hand with Magnolia collection. The collection, available in stores and online, features 300 pieces including bedding and lifestyle products. In February 2019, Joanna created an exclusive collection for Anthropologie of "globally inspired" rugs and pillows.
On April 10, 2019, Chip and Joanna announced the launch of a'new media company.' Chip and Joanna Gaines will serve as chief creative officers and current HGTV president Allison Page will serve as president of the new joint venture, which will include a TV network and a streaming app. In November 2019, Chip and Joanna opened Magnolia Press, in Waco, Texas; this new store is in addition to two others that they have, Magnolia Table and Silos Baking Co. Fixer Upper is credited with the rise in popularity of "Farmhouse-chic" interior design in the late 2010s. In 2018, Zillow reported that homes with architectural features mentioned on the show, such as wainscoting, clawfoot bathtubs, barn doors, sold at an average of 30 percent above expected value. In addition, the show has generated an increase in tourism and economic development in Waco, where the show was filmed. Thanks to the show's popularity, the homes featured on the show have become desirable to either purchase or rent. At least six of the homes are available to rent through Airbnb or VRBO.
Owners are renting them for anywhere from $250 to $350 a night. Selling the homes renovated by the Gaines has become a way for show participants to make a profit; the Bicycle House featured in Season 1, Episode 12 went up for sale in 2016 for $350,000 after being purchased for less than $50,000. It was available for rent on VRBO for $250 a night; the Barndominium featured in Season 3, Episode 6 went up for sale in April 2017 for $1.2 million. The Barndominium's owner was found guilty of a misdemeanor and fined $1 in November 2017 for renting out the home after being denied a vacation rental permit by the city; the owner intended to appeal the verdict. On April 27, 2017, Chip Gaines was named in a fraud lawsuit filed by former business partners; the former partners alleged that the Gaineses persuaded them to sell their interest in Magnolia Realty to him for $2,500 each without disclosing plans, in the works to develop the Fixer Upper reality television show. His attorney, Jordan Mayfield, told KWTX-TV, the CBS television station in Waco, Texas, “We are confident that these claims will be found to be meritless, it is disappointing to see people try to take advantage of the hard work and success of Chip and Joanna Gaines."In another matter, in June 2017, it was announced that they "settled with the United States Environmental Protection Agency over allegations that they violated rules for the safe handling of lead paint during home renovations."
They paid $40,000 in fines and will comply with such regulations going forward, "remain committed to raising awareness in our community and our industry." Fixer Upper on HGTV Fixer Upper on IMDb
Maurice Edward Youmans is a former American football defensive end in the National Football League for the Chicago Bears and Dallas Cowboys. He played college football at Syracuse University. Youmans attended North Syracuse High School, where he focused on playing basketball and averaged 20 points a game, he started playing football as a senior. After graduating, he spent one year at Dean Academy to improve his grades, he accepted a scholarship from Syracuse University and was redshirted as a junior after having back surgery. As a senior, he became part of a defensive/offensive line known as the "sizeable seven" that included Bob Yates, Fred Mautino, Al Bemiller, Roger Davis, Bruce Tarbox and Gerry Skonieczki, he blocked for Ernie Davis and was a member of the undefeated national championship team in 1959. He lettered in basketball, where he was a backup at center as a sophomore and senior. Youmans was selected by the Chicago Bears in the ninth round of the 1959 NFL Draft with a future draft pick, which allowed the team to draft him before his college eligibility was over.
As a rookie, he played left defensive end and his bookend partner was future hall of famer Doug Atkins, but missed games with a dislocated shoulder. After playing all of the games in 1962, the next season he was missed 8 games. In 1963, he was placed on the injured reserve list with a knee injury, complicated by a serious infection, he would end up missing the season. The next year, he requested a trade thinking he was going to the Green Bay Packers, but instead was sent to the Dallas Cowboys in exchange for offensive end Gary Barnes on June 18, 1964. In 1964, he was the defensive line's top backup and started the last 3 games in place of an injured Larry Stephens; the next season, he was the regular starter at left defensive end, but was limited with an unstable knee. After being selected by the Atlanta Falcons in the 1966 NFL expansion draft, he was traded to the New York Giants. A knee operation didn't allow him to participate in the New York Giants training camp and was released on September 6, 1966.
Super Entrances for a Football Giant
The 2015 Eschborn-Frankfurt City Loop was scheduled to be the 54th edition of the Eschborn-Frankfurt City Loop semi-classic cycling race. The race was cancelled the day before it was scheduled to take place because of a suspected terrorist plot similar to the Boston Marathon bombing; the race was to have taken place on 1 May 2015 and was rated as a 1. HC event by the Union Cycliste Internationale; the planned route was starting in Eschborn and ending in Frankfurt. The defending champion was Alexander Kristoff; the favourites for victory included Kristoff and John Degenkolb, who had between them won the Milan–San Remo, the Tour of Flanders and the Paris–Roubaix. 22 teams were invited to take part in the race. Six of these were UCI WorldTeams. On 30 April 2015, the day before the race was due to have taken place, local authorities announced that it had been cancelled due to "indications of a possible threat to the population". A couple, one of whom was described as a "suspected Islamic extremist", were arrested the previous day at their home in Oberursel, along the race route.
The couple arrested were identified as Halil D. 35, a German citizen of Turkish origin, Senay D. 34, thought to be a Turkish citizen. Various items were found in their house, including a homemade pipe bomb, bomb-making materials, an automatic rifle, bazooka ammunition and a canister full of petrol. One of the couple had bought hydrogen peroxide and alcohol at a hardware shop and had been seen exploring a forest along the race route, he had connections to Salafists in Frankfurt, including the group Dawa FFM. The German newspaper Die Welt suggested that he was involved with Al-Qaida Al-Qaeda in the Islamic Maghreb. According to German police the couple had travelled to Spain to meet with members of Sharia4Spain, it has been suggested that there may have been connections to Adem Yilmaz, one of those convicted as part of a bomb plot in 2007. Security officials suggested that the couple may have been planning an attack similar to the 2013 Boston Marathon bombing. Halil D. was sentenced to two and a half years in prison in July 2016 for possession of illegal weapons and falsification of documents.
Akshay Bhatia is an American professional golfer. Bhatia was born in Northridge and lives in Wake Forest, North Carolina, he was runner-up at the 2018 U. S. Junior Amateur, he won two silver medals at the 2018 Summer Youth Olympics in the boy's individual and the mixed team with Lucy Li. He played on the Junior Presidents Cup team in 2017 and Junior Ryder Cup in 2018, with both teams winning. Homeschooled, Bhatia intends to forgo college and turn professional upon turning 18. Bhatia made his PGA Tour debut at the 2019 Valspar Championship on a sponsorship exemption. Bhatia made his Web.com Tour debut on April 18, 2019 at the Robert Trent Jones Golf Trail Championship, where he made the cut and finished T-42. Bhatia turned professional in September 2019 after competing in the 2019 Walker Cup, made his professional debut at the Sanderson Farms Championship. 2016 AJGA - CJGT Junior at Yorba Linda, IZOD AJGA Championship 2017 Davis Love III Junior Open, Junior PGA Championship, AJGA Junior at Ford's Colony 2018 Junior Invitational at Sage Valley, Polo Golf Junior Classic, Boy's Junior PGA Championship, Rolex Tournament of Champions 2019 Jones Cup Invitational, Dustin Johnson World Junior ChampionshipSource: Junior Presidents Cup: 2017 Junior Ryder Cup: 2018 Walker Cup: 2019 Source