Halogenation is a chemical reaction that involves the addition of one or more halogens to a compound or material. The pathway and stoichiometry of halogenation depends on the structural features and functional groups of the organic substrate, as well as on the specific halogen. Inorganic compounds such as metals undergo halogenation. Several pathways exist for the halogenation of organic compounds, including free radical halogenation, ketone halogenation, electrophilic halogenation, halogen addition reaction; the structure of the substrate is one factor. Saturated hydrocarbons do not add halogens but undergo free radical halogenation, involving substitution of hydrogen atoms by halogen; the regiochemistry of the halogenation of alkanes is determined by the relative weakness of the available C–H bonds. The preference for reaction at tertiary and secondary positions results from greater stability of the corresponding free radicals and the transition state leading to them. Free radical halogenation is used for the industrial production of chlorinated methanes: CH4 + Cl2 → CH3Cl + HClRearrangement accompany such free radical reactions.
Unsaturated compounds alkenes and alkynes, add halogens: RCH=CHR′ + X2 → RCHX–CHXR′The addition of halogens to alkenes proceeds via intermediate halonium ions. In special cases, such intermediates have been isolated. Aromatic compounds are subject to electrophilic halogenation: RC6H5 + X2 → HX + RC6H4XThis reaction works only for chlorine and bromine and is carried in the presence of a Lewis acid such as FeX3; the role of the Lewis acid is to polarize the halogen-halogen bond, making the halogen molecule more electrophilic. Industrially, this is done by treating the aromatic compound with X2 in the presence of iron metal; when the halogen is pumped into the reaction vessel, it reacts with iron, generating FeX3 in catalytic amounts. The reaction mechanism can be represented as follows: Because fluorine is reactive, the protocol described above would not be efficient as the aromatic molecule would react destructively with F2. Therefore, other methods, such as the Balz–Schiemann reaction, must be used to prepare fluorinated aromatic compounds.
For iodine, oxidising conditions must be used in order to perform iodination. Because iodination is a reversible process, the products have to be removed from the reaction medium in order to drive the reaction forward, see Le Chatelier's principle; this can be done by conducting the reaction in the presence of an oxidising agent that oxidises HI to I2, thus removing HI from the reaction and generating more iodine that can further react. The reaction steps involved in iodination are the following: Another method to obtain aromatic iodides is the Sandmeyer reaction. In the Hunsdiecker reaction, from carboxylic acids are converted to the chain-shortened halide; the carboxylic acid is first converted to its silver salt, oxidized with halogen: RCO2Ag + Br2 → RBr + CO2 + AgBrThe Sandmeyer reaction is used to give aryl halides from diazonium salts, which are obtained from anilines. In the Hell–Volhard–Zelinsky halogenation, carboxylic acids are alpha-halogenated. In oxychlorination, the combination of hydrogen chloride and oxygen serves as the equivalent of chlorine, as illustrated by this route to dichloroethane: 2 HCl + CH2=CH2 + 1⁄2 O2 → ClCH2CH2Cl + H2O The facility of halogenation is influenced by the halogen.
Fluorine and chlorine are more aggressive halogenating agents. Bromine is a weaker halogenating agent than both fluorine and chlorine, while iodine is the least reactive of them all; the facility of dehydrohalogenation follows the reverse trend: iodine is most removed from organic compounds, organofluorine compounds are stable. Organic compounds and unsaturated alike, react usually explosively, with fluorine. Fluorination with elemental fluorine requires specialised conditions and apparatus. Many commercially important organic compounds are fluorinated electrochemically using hydrogen fluoride as the source of fluorine; the method is called electrochemical fluorination. Aside from F2 and its electrochemically generated equivalent, a variety of fluorinating reagents are known such as xenon difluoride and cobalt fluoride. Chlorination is highly exothermic. Both saturated and unsaturated compounds react directly with chlorine, the former requiring UV light to initiate homolysis of chlorine. Chlorination is conducted on a large scale industrially.
Bromination is more selective than chlorination. Most bromination is conducted by the addition of Br2 to alkenes. An example of bromination is the organic synthesis of the anesthetic halothane from trichloroethylene: Organobromine compounds are the most common organohalides in nature, their formation is catalyzed by the enzyme bromoperoxidase which utilizes bromide in combination with oxygen as an oxidant. The oceans are estimated to release 1–2 million tons of bromoform and 56,000 tons of bromomethane annually. Iodine is reluctant to react with most organic compounds; the addition of iodine to alkenes is the basis of the analytical method called the iodine number, a measure of the degree of unsaturation for fats. The iodoform reaction involves degradation of methyl ketones. All elements aside from argon and helium form fluorides by direct reaction with fluorine. Chlorine is more selective, but still reacts with most metals and heavier nonmetals. Following the usual trend, bromine is less iodine least of all.
Of the many react
Hastings Historical Society Museum is a heritage-listed former retail store and now museum at 22 Clarence Street, Port Macquarie, Port Macquarie-Hastings Council, New South Wales, Australia. It was built from 1835 to 1840 by William Stokes, it is known as Port Macquarie Historical Society Museum and Port Macquarie Museum. It was added to the New South Wales State Heritage Register on 2 April 1999; the museum building was used as a store until well into the twentieth century. The block of land on which the Museum now stands was purchased at auction by Edward McRoberts on 14 February 1834 for 13 pounds 8 shillings, 8 pence; the titles were issued to him on 22 December 1834. The older western portion of this building was erected between 1835 and 1840, it was owned by Mr W. Stokes sometime after 1834 but little is known until 17 January 1853 when Samuel H. and Elizabeth Cohen, sold out to William Killion, another storekeeper, for 75 pounds. He in turn sold out to another storekeeper, James H. Young on 25 January 1868 for 60 pounds.
Young sold to Francis Marchment on 6 September 1881 for 120 pounds and it was about this time that the eastern section was added. The property remained in the marchment family until sold to A. P. Hayward on 14 January 1925. Francis Marchment occupied this building from 1881 to 1925, he immigrated from Gloucestershire in 1862 and arrived in Port Macquarie in 1869 with his partner George Day. They procured a 3 tonne cutter and traded extensively on the Hastings River to Rawdon Island and Beechwood. Day sold out after a short time. Trade was chiefly by barter, the settlers providing cedar logs, hides and corn in return for sugar, tea and clothes; the cedar logs were towed in rafts behind the cutter. His traders horn was a welcome sound to the settlers along the river, as his cutter was the only contact with the outside world and for fresh supplies, he met his wife Christina Newberry 1855-1911 at Rawdon Island. There was a family of two daughters most of whom were born in this building, it was taken over by the Hastings Historical Society in 1959 and progressively reconstructed with major additions in 1968 and 1977.
During the initial renovations and restoration evidence of alterations during its earlier existence were found together with foundation bricks bearing arrows and other convict marks. Extensions have been made to accommodate additional research and display areas and office space. In 2013 the Society commissioned a Cultural Tourism Plan from Kevin Williams of Sydney Scenes, with a grant from the NSW Office of Environment and Heritage. A copy was lodged with the Heritage Council in 2014 and it made recommendations to improve the museum's sustainability; the architectural style is Old Colonial Georgian. It is a simple two-story building of painted brick construction with hipped iron roof over the original shingles and two chimneys; the roof was gable, but changed when a 13 ft extension was made to the eastern end of the building in the late nineteenth century. This extension involved the removal of an internal staircase attached to the eastern wall. A skillion kitchen extended along the southern wall of the building.
Ceilings and upstairs internal walls are boarded. The building was derelict when leased by the Hastings District Historical Society in 1959. Restoration included new flooring to the ground floor, new staircase and guttering, replacement of fireplace surrounds, erection of an annexe. Major extensions were made on the south side in 1968 and in 1977. There were further extensions to the rear of the building in 1988; the physical condition of the building was reported as excellent as at 11 October 2004. The archaeological potential is medium. Underfloor deposits of convict built bricks have been found during renovation and evidence of earlier building alterations. 1834 - store built 1880s - extension to eastern end of building 1959 - renovated 1968 - extension on the south side 1977 - extension on the south side 1988 - further extensions to the rear of the building The museum building demonstrates the form scale and style of development which took place when free settlement was permitted in Port Macquarie.
One of the only surviving early commercial and residential buildings in Port Macquarie. Located near other historic buildings such as the Courthouse and The Garrison; as a museum it continues to provide a focus for historical research and heritage within the community. Hastings Historical Society Museum was listed on the New South Wales State Heritage Register on 2 April 1999. "Museum - Tourism Website". 2007. Cutter, Deryck. NSW State Heritage Inventory Form. Port Macquarie-Hastings Council. "Museum - Tourism Website". Suters Architects Snell. Municipality of Hastings Heritage Study; this Wikipedia article was based on Hastings Historical Society Museum, entry number 00326 in the New South Wales State Heritage Register published by the State of New South Wales and Office of Environment and Heritage 2018 under CC-BY 4.0 licence, accessed on 1 June 2018
Mass graves in Ljubljana were created in Ljubljana, Slovenia during and after the Second World War. The Commission on Concealed Mass Graves in Slovenia has registered five known mass graves in the city itself and an additional 15 in the City Municipality of Ljubljana. Except for the Orel Peak Mass Grave, a former wartime Home Guard cemetery, all of the concealed mass graves in Ljubljana were created in the immediate aftermath of the Second World War, after British forces forcibly repatriated Home Guard soldiers that had fled to Austria to Yugoslavia from camps in Bleiburg, Rosenbach and elsewhere. Many of the returnees were held at the St. Stanislaus Institute in the former village of Šentvid, just outside Ljubljana, used as a prison by the Partisans; some died in Šentvid. Five mass graves registered by the Commission on Concealed Mass Graves in Slovenia are located inside the city limits: The Orel Peak Mass Grave is located at the southeast end of Castle Hill in central Ljubljana, about 580 m from Ljubljana Castle.
It is the site of a former military cemetery for 146 Home Guard soldiers that could not be buried in their home cemeteries due to circumstances during the war. Burials took place at the site from December 1943 until the end of April 1945, a large-scale commemoration was held at the cemetery on All Saint's Day in 1944. After the war, the cemetery was destroyed and most of the remains were removed to an unknown location. Memorial crosses erected at the site since 1991 have been vandalized. There is a chapel-shrine near the site, dating from before the First World War, where an annual memorial service is held; the Big Brezar Shaft Mass Grave is located in the Kucja Valley on the northwest outskirts of the city. It contained the remains of a mix of Slovenian and Croatian prisoners of war from the St. Stanislaus Institute in nearby Šentvid and civilians, including women; the Kucja Valley Mass Grave lies below the Big Brezar Shaft Mass Grave. After seepage from the Big Brezar Shaft poisoned the groundwater in the area, German prisoners of war were forced to remove the bodies from the shaft on 12 and 13 June 1945 and bury them in the nearby mass grave at the head of the Kucja Valley.
After this, the German prisoners were executed and buried together with the bodies they had moved. The Šentvid 1 Mass Grave is located a few meters outside the cemetery wall in the Šentvid District, in the northwest part of the city, near the spot where a large oak tree fell during a storm in 1986, it contains the remains of Home Guard prisoners of war that were returned to Yugoslavia by British forces from prisoner of war camps in Austria but died before they could be transported to the Kočevje area, where most of them were murdered. The Šentvid 2 Mass Grave is located a few meters from the first grave and contains the remains of German prisoners of war and wounded prisoners; the Society for the Regulation of Concealed Graves installed a pair of plaques on the Šentvid cemetery wall facing the graves in 2002. They read: "The victims of violence from the Partisan collection center in Šentvid lie and await the resurrection behind this wall. In memory of the victims, a warning to the living," and quote the Book of Wisdom: "For though they be punished in the sight of men, yet is their hope full of immortality.
And having been a little chastised, they shall be rewarded: for God proved them, found them worthy for himself." Other victims from the prison in Šentvid were killed outside Ljubljana, in Glažuta, Golo and Setnica. An additional mass grave in the city is located in Dobrunje, but has not been registered by the commission; the memorial site at Saint Ulrich’s Church is believed to contain the remains of people liquidated by the Partisans during or after the war, including the "Šentpavel victims" —eight men abducted by Yugoslav military police from the village of Šentpavel on 4 July 1945 and murdered. Fifteen additional mass graves are located in the City Municipality of Ljubljana outside the Ljubljana city limits. There are four graves in Pance and 11 graves in Selo pri Pancah
Pierre Denan is the author of Pourquoi Tom Cruise: Book 1, Pourquoi Tom Cruise: Book 2 news ticker tales published by les Presses du réel as part of their Literature Collection—Fiction. He has published: Libre and Voilà, A Collection, Notes for the Book to Come, his artwork is exhibited on the Internet and in artists's publications. His books on art include Poulet Poulet, R. Thomas, JE, Dragon Eye, he has contributed to Grams of Art, AH AH AH. His paintings represent the bulk of his visual diary, are gathered in Pierre Denan Diary: A Selection of Works, published by Presses du réel in 2014, their formal vocabulary has been borrowed from Steven Parrino—though they have dropped the American artist's dramatic, deathlike dimension, as well as his elements of mannerism and folkloric post-punk and biker spirit. In 2000 he created a press devoted to contemporary art. Since he has acted as both editor and artistic director for art books and journals such as: MAP, AH AH AH a creative journal, 20/27 a critical art review, 2870 Grams of Art an art journal, I.
S. Inventaire Supplémentaire, a collection of art books. Pierre Denan is the author of Pourquoi Tom Cruise, a text with which he defined the "news ticker tale" concept, a genre inspired by the continuous display of news items at the bottom of some news channel screens. Book 1 was published in 2010, he is the author of Libre –a series of four texts that were printed as booklets and made available to the public in galleries and other Paris-based contemporary art venues from 2002 to 2005–, of Paradis, Voilà, A Collection, Notes for the Book to Come. His artwork is exhibited at Multiples Gallery, Paris, on the Internet, in art journals, he is the author of artist's books. The generic titles of the different open works in progress in the framework of his art are: "Opening themes series", "Variations Marshall", "Miss Manga Project". According to the artist, Miss Manga, a manipulated, monochromatic painting, forms the central part of his visual journal; this artwork is in part gathered in a Selection of Works.
In 2000 he created M19 Editions, devoted to contemporary art. The aim is for artists to release their unpublished works and art historians to generate studies on art, in progress, as well as "to bring theoretical criticism to the panorama of francophone reviews and direct access to artworks". Denan publishes books and journals, acting as both editor and art director. In 2015, he founded JakeAfterShow, a creative studio, whose name evokes the legend of an image of Jake, a guy we can imagine sitting on a couch after a fashion show, a party photographed by Nan Goldin—, which has the following baseline: we make stories, it will produce a print and web magazine in 2017. About Pourquoi Tom Cruise, Denan has written:The news ticker tale Pourquoi Tom Cruise is a stroke, a flow with a form inspired by the continuous display of titles and dispatching of new media on the news channel screens, it is a narrative composed of elements hailing from online newsfeeds—a hot spot for fiction—, borrowings from literature, references to films and art, but of a whole fictional, original context.
It is characterized by the predictability of its contents, ceaselessly reverting to what has been uttered. As the tale’s main character—and non-subject—Tom Cruise incarnates the paranoid, terrorized, young, sustainable hyperme of our hypermodern times. Here is a hyperCruise, a hypercharacter, the absolute trademark of "modernity heightened to a superlative power", but the mask behind which I write my own song. Pierre Denan 2002–2005 Libre, M19 2003 Libre in Bordel n° 3 fr:Bordel, Paris 2010 Pourquoi Tom Cruise, book 1, Les presses du Réel, Dijon 2010-today Pierre Denan websites and social networks 2015 Pourquoi Tom Cruise, book 2, Les presses du Réel, Dijon 2015 Paradis in Le Cafard Hérétique, n° 5, 2016 Pourquoi Tom Cruise, book 2, Palais de Tokyo, Paris 2016 Voilà, Une collection, work in progress, forthcoming 2016 Pourquoi Tom Cruise, Centre Pompidou, September 15 2018 Pourquoi Tom Cruise, book 3 2018-2020 Journal, Pierre Denan Journal 1998 Personnes en quête d’un divertissement, short-film 2002 Poulet Poulet, artist book, M19 2002 R. Thomas, artist book, I.
S. Inventaire Supplémentaire collection, M19 2003 JE, artist book, M19 2005 Dragon Eye, artist book, M19 2005 Come Again, performances at Galerie du Forum and Les Abattoirs, Toulouse 2007 2860 Grams of art, artists's magazine, M19 2008 2870 Grams of art, artists's magazine, M19 2010-today Pierre Denan websites and social networks 2011 AH AH AH, artists's magazine, M19, read the magazine online 2011 Pour le Mur, solo show, Galerie de Multiples, Paris 2014 Pierre Denan Diary, a selection of works, Les presses du réel, Dijon 2015 « Mauvais Genre » exhibition, group show, Addict Gallery, Paris 2017 « Road is a road is a road… » exhibition, group show, GDM Galerie de Multiples, Paris 2017 « Culbuteurs » exhibition, group show, Le Garage, Paris 2018 « Blind-Marché », a group show curated by Samuel Boutruche for Le Consultat, Paris 2019 « It’s a Wonderful Life », Group Show, Gilles Drouault Galerie/Multiples 2000 The birth of M19 editions 2000–2004 MAP, contemporary art critic, M19 2002–2009 « I.
S. Inventaire Supplémentaire » collection, artists's books, M19 2007 2860 Grams of art, artists's magazine, M19 2008 2870 Grams of art, artists's magazine
South Carolina Gamecocks football under Steve Spurrier covers the history of the South Carolina Gamecocks football program under Steve Spurrier from 2005 to 2015. Former Washington Redskins head coach Steve Spurrier, who achieved fame after a successful stint as head coach at his alma mater Florida, was hired in 2005 to replace the retiring Lou Holtz. Spurrier led the Gamecocks to a 7 -- Independence Bowl appearance in his first season; as a result, Spurrier was named the 2005 SEC Coach of the Year. The 2006 season saw continued success under Spurrier, as the Gamecocks posted an 8–5 record and a victory over Houston in the Liberty Bowl. In 2007, the Gamecocks would lose all of their next five games; the team was not selected for a bowl game. South Carolina posted consecutive 7–6 records in 2008 and 2009, returning to postseason play with appearances in the Outback Bowl and PapaJohns.com Bowl. In 2010, Spurrier scored another first with the first SEC Eastern Division Championship in school history.
On November 13, 2010, the Gamecocks defeated Florida 36–14 to clinch the division. Prior to this contest, USC had an all-time record of 0–12 at The Swamp. Freshman RB Marcus Lattimore rushed for 3 touchdowns in the game. Spurrier got his first win in Gainesville as a Gamecock, received a "Gatorade Bath" from his players, became the first coach to win the SEC East with two different teams. Earlier in the season, the Gamecocks posted the program's first win over a No. 1 team in program history, with a 35–21 victory over top-ranked, defending national champion Alabama. In 2011, Spurrier led USC to its most successful season in program history; the Gamecocks posted an 11–2 overall record, went 6–2 in SEC play, defeated No. 20 Nebraska in the Capital One Bowl to earn Final Top 10 rankings in the AP and Coaches' Polls. Along the way, USC defeated Georgia, Tennessee and Clemson in the same season for the first time in program history; the University of South Carolina was investigated in 2011–12 by the NCAA after it came to light that student-athletes had received an estimated $59,000 in impermissible benefits the result of discounted living expenses at a local hotel.
The school imposed its own punishment, paying $18,500 in fines and cutting three football scholarships in each of the 2013 and 2014 seasons. The school reduced its official visits for the 2012–13 year, from 56 to 30; the NCAA ruled this self-imposed punishment as adequate, stating that "the violations were limited in scope" and "there was no unethical conduct in this case", went on to praise the school's handling of the affair, with the chairman of the NCAA infractions committee stating, "This has been one of the best cases I have seen from a process standpoint.... In this case, it was obvious to the committee that the university wanted to get to the truth." The commissioner went on to state that USC "wanted to ask all the hard questions of all the right people and, in some cases, they went beyond what the NCAA staff was doing." In 2012 Steve Spurrier, once again, led his South Carolina football team to double-digit wins during the course of the regular season campaign. The 2012 regular season culminated with the annual season-ending game against arch-rival Clemson at Clemson's Memorial Stadium.
Spurrier and his Gamecocks emerged with a fourth consecutive victory over the Tigers – a victory marked by Spurrier winning his 65th game at Carolina and, in doing so, becoming the winningest coach in Gamecock football history surpassing Rex Enright's 64-win total. Spurrier led the Gamecocks to a thrilling 33–28 victory in the Outback Bowl against the winningest program in college football, Michigan; the victory elevated the Gamecocks to an 11–2 record for the second consecutive season. Additionally, by finishing 8th in the Associated Press poll and 7th in the Coaches poll, South Carolina finished in Top 10 of both polls for the second consecutive year. In 2013, Spurrier and the Gamecocks finished with another successful 11–2 season; the season started off with a convincing 27–10 win over North Carolina, although they fell to Georgia for the first time in four years, 41–30. Carolina went on a four-game winning streak before falling to Tennessee in Knoxville after starting quarterback Connor Shaw left the game with a knee injury.
In the following game against division-leading #5 Missouri, Shaw was sidelined due to injury, backup Dylan Thompson got the start. After a weak performance from the Gamecocks in the first three quarters, Shaw was put in the game in the fourth quarter with South Carolina down 0–17. Shaw went on to lead a historic comeback in which the Gamecocks beat Missouri in double overtime, 27–24; that game was the first of a six-game winning streak in which Spurrier and Carolina won the rest of their games, posting another 11–2 season. In the highest-ranked meeting of rivals, the #9 Gamecocks defeated #4 Clemson for the fifth year in a row, a school record, by a score of 31–17. Spurrier led the Gamecocks to a 34–22 victory over the #19 Wisconsin in the 2014 Capital One Bowl. South Carolina finished with the highest ranking in school history in the AP poll, ranked at #4 in the country. South Carolina opened the 2014 season at home against Texas A&M, the Aggies' 52–28 upset over the #9 Gamecocks snapped college football's longest active home winning streak.
Carolina earned a measure of redemption two weeks knocking off the #6 Georgia Bulldogs at home. Two weeks the 13th-ranked Gamecocks would again suffer a home upset, falling to Missouri, 21–20; this loss dropped USC out of the top 25 for the first time since the 2010 season. The Gamecocks closed out the regular season with their first loss in six years to their
"If You Want It" is the thirty-first UK single from synthpop group Orchestral Manoeuvres in the Dark, released in September 2010 by 100% Records as the first single from their eleventh studio album "History of Modern". It is the band's first single since "Universal" in 1996, is the first single with the original line-up since "Dreaming" in 1988; the song was a top 50 hit in Germany. The track was previewed, along with "History of Modern" on their website during August and was announced as the album's first single; the artwork was revealed that month. The music video for "If You Want It" was released on the band's website on 16 August 2010, it shows a group of dancers performing underneath the spotlight while the two band members watch the display. "If You Want It" – 4:42 "Alone" – 4:24 "If You Want It" – 4:24 "If You Want It" – 3:25 "If You Want It" – 3:59 "Idea 1" "If You Want It" – 3:47 "If You Want It" – 5:04 "If You Want It" – 4:24 "If You Want It" – 3:24 "If You Want It" – 4:10 "If You Want It" – 6:29 Toby Harris – sleeve design Peter Saville – design Robin Schmidt – mastering Mike Crossey – mixing, OMD* Morgan Price – additional mixing Oliver Buchannan – additional mixing Guy Katsav – mixing, additional programming OMD – production, mixing All tracks mastered at 24-96 Mastering Recorded and mixed at The Motor Museum Studio, Liverpool OMD - If You Want It - Official Video on YouTube "If You Want It" at Discogs