For price sensitive bus automatic payment and access control system, Plus breakthrough significance in terms of security and performance. Relative to the Classic, Plus a higher level of security.
Higher security is the core of the Plus advantages. It USES the length of a 128bit key authentication and encryption AES algorithm. At the same time, the Plus on architecture also contains a series of other security features, for example, Plus at the same time use random card serial number (RIDs) and 7bytes (UIDs)global unique serial number,can be used to protect the user's information.
Plus has including the advanced encryption standard (AES) encryption technology, multiple security, at the same time can help customers from the current Classic deployment is convenient to upgrade, after the system upgrade, the operator can easily will rise card security level, Without the card issuer. Compatible with both the S50 and S70 cards, compatible with NFC technology,the increased security.
Plus divided into S (standard) and X (enhanced) two versions, each version distribution has 2 k and 4 k storage capacity of two models.
Card can provide white card, printing, paper sticker, key chain, wristbands, TOKEN, and there are many kinds of sizes and the thin and thick.ODM and OEM products according to customer's demand.
Applications: access control, time and attendance, meeting attendance, identification, logistics, industrial automation, various membership cards, such as Canteen, subway, bus tokens cards, clubs and other consumer electronics, electronic tickets, animal identification, target tracking, laundry management, a variety of card and so on.


text:
Cherokee Phoenix continues to soar
Teri Saylor
Special to Publishers' Auxiliary
The legend of the mythical phoenix is one of rebirth and renewal. And in the Cherokee Nation, the storied Cherokee Phoenix newspaper has lived up to its name for nearly 200 years.
The Cherokee Phoenix, an independent community newspaper owned by the Cherokee Nation and published twice a month, is coming off a banner year in almost every area of publishing, from news coverage to circulation to awards.
The newspaper comes out in print and has a vibrant online presence with no paywall.
Executive editor Tyler Thomas is planted in both the journalism and the business sides, working closely with the assistant editor to oversee news coverage. He also manages his advertising team and stays on top of the newspaper's budget.
"I work diligently with the finance team to make sure we are always where we need to be," he said in a recent Zoom interview.
In addition to revenue generated through subscriptions and advertising, the Cherokee Nation supports the newspaper financially.
Thomas is a Cherokee Nation citizen, born and raised, his roots running deep within the tribe, which the largest Native American tribe in the United States with more than 440,000 citizens worldwide.
Over 141,000 of those Cherokee Nation citizens reside within the tribe's reservation boundaries — an area comprised of 14 counties in northeastern Oklahoma.
It's a vast community for a bi-weekly newspaper to cover with a staff of 12 people, including Thomas.
THRIVING THROUGHOUT A TUMULTUOUS HISTORY
The Cherokee Phoenix has been serving readers for 194 years. Its history is published on its website.
Launched on February 21, 1828, the Cherokee Phoenix was published in New Echota, Georgia, which was then the Cherokee Nation's capital. The bilingual newspaper was published in both English and Cherokee. A year after it launched, its nameplate was extended to The Cherokee Phoenix and Indian Advocate.
In the 1830s, editor Elias Boudinot and Principal Chief John Ross used the newspaper to editorialize against the Indian Removal Act of 1830 and the growing encroachment and harassment of European settlers in Georgia. Financial troubles, coupled with a rampage by the Georgia Guard, which destroyed the press and burned the newspaper's office, silenced the Phoenix for several years during the Trail of Tears era. In the ensuing decades of turmoil when state and federal governments attempted to dissolve native governments, the newspaper rose and fell until the 1970s, when the Cherokee Nation stabilized in its modern form.
"And then the newspaper came back but continued to struggle, mostly due to financial issues, before finally getting its footing in the '80s," Thomas said.
In October 2000, the Tribal Council passed the Cherokee Independent Press Act of 2000, which ensures the coverage of tribal government and news of the Cherokee Nation is free from political control and undue influence, and by 2007, the newspaper had begun using the original Cherokee Phoenix nameplate.
Today, the newspaper reports on the tribe's government; current events; and Cherokee culture, people and history. The news organization has also broadened its outreach to include locally aired radio shows and social media.
While the Cherokee Nation owns the newspaper, the editors and reporters enjoy independent press freedom and protections from political influence, Thomas said.
"We have the freedom to operate as we see fit and report as we see fit, without the fear of being fired or reprimanded or anything like that," he said.
Over the years, the Cherokee Nation has passed a reporter's privilege, a Freedom of Information Act and other right-to-know laws. In addition, the newspaper enjoys the press freedom provided by the United States federal government and Oklahoma state laws.
DEEPLY ROOTED IN ADVOCACY
Published in print on the first and 15th of each month, you might say the Cherokee Phoenix is a community newspaper on steroids, committed to fiercely covering its vast community.
"We write a lot of stories that focus on our 14-county reservation, but with nearly a half million citizens worldwide, our coverage is expansive," Thomas said. "We cover people that are doing amazing things everywhere, from the West Coast to the East Coast and even abroad."
While the Phoenix has a broad geographic footprint, it is narrow in its scope of coverage, sticking to reporting on issues specific to the Cherokee Nation, Thomas said.
"We leave coverage of city and county government to the other local newspapers," he said. "While some of our readers might find that coverage helpful, we simply don't have the staff to do it."
Readership is strong, running over 200,000, thanks to a boost by the Cherokee Nation, which used funding from the American Rescue Plan (ARPA) to purchase subscriptions for all Cherokee Nation households across the United States in 2022. Thomas expects circulation to drop in 2023, when the free subscriptions become premiums for readers who opt in to join a website that will link them to information about government services. Those who don't opt in can purchase subscriptions.
In addition to the newspaper's print circulation, web traffic runs anywhere from 80,000 to 100,000, Thomas said.
Harkening back to its advocacy roots, the newspaper has been reporting on and calling for the U.S. House of Representatives to seat Kimberly Teehee, the Cherokee Nation's first delegate in history, a measure guaranteed in the 1835 Treaty of New Echota, enacted by the United States during the forced removal of the Cherokees from their homelands.
Principal Chief Chuck Hosking Jr. appointed Teehee in 2019. The House has had recent hearings on the matter, but as of December had not voted on seating her.
"It's been little over three years now since Delegate Teehee was named, and the House finally had the hearing in November," Thomas said. "There's a lot of interest in it just because of the magnitude of the story. People near and far are very interested in it because it's something that not only benefits Cherokee Nation; it benefits all of Indian country."
And there has been a great deal of support from non-native people, too.
"I saw Pearl Jam tweet the other day in support of Delegate Teehee, and I think the actor, Mark Ruffalo, has tweeted in support of it," Thomas said.
The Cherokee Nation delegate and other delegates representing the District of Columbia, Puerto Rico and four inhabited U.S. territories can hold ex-officio seats in the U.S. House. While they may be assigned to committees, can submit amendments to bills, and participate in floor debates, they cannot vote on laws.
"You're seeing it on the local level and nationwide that many people want to see the government held to their word and uphold a promise that was made hundreds of years ago," Thomas said.
The newspaper has also been a strong advocate for continued sovereignty of the Cherokee Nation, jurisdiction over its land and its ability to govern.
The newspaper has been closely monitoring a Supreme Court case on the constitutionality of the Indian Child Welfare Act. The law, established in 1978 and under threat today, enables Native governments to participate in child welfare cases involving Native children and prioritizes their placement with family or extended kin.
"It is an issue that can set a precedent that extends well beyond the Indian Child Welfare Act," Thomas said. "It could extend to other sovereignty issues and how tribes operate and govern."
SERVING A VAST COMMUNITY
The Cherokee Phoenix has a vast yet close-knit readership that Thomas compares to a family, and he believes future success lies in understanding readers. While the print version of the newspaper will always be its cornerstone, digital media will be its future, he says.
"Print is what we're known for, and it's what our foundation is built upon," he said "As technology continues to evolve, we have to evolve too, because we need to understand that while our 60-year-old citizens rely on the print copy for their news consumption, the 25-year-olds are gravitating to digital platforms and apps."
No paywall, free subscriptions for readers and financial support by the owner certainly pave the way for success, but just like any other newspaper, the Cherokee Phoenix is not without its challenges — particularly with advertising in the post-pandemic economy. Thomas believes that support benefits readers in the end.
"We aren't as out in the wind as some of the traditional non-native newspapers because we do have some security and support from tribal funding, so we haven't had to deal with layoffs or anything like that," he said. "And that benefits our citizens because we are able to give them the news they expect and that they need."
Today, Thomas is celebrating a banner awards year. The newspaper was a finalist for Newspaper of the Year in the Great Plains Journalism Awards, was named as the best newspaper in Oklahoma's SPJ awards and won first place for general excellence in the National Native American Journalist Association Awards.
"It's always a good feeling whenever other organizations affirm our work," he said. "I always say I have the best news team in the country. And I truly do believe that."
For all the awards, subscription promotions and interesting news coverage, the history of the Cherokee Phoenix and its mission are never far from Thomas' heart.
"It's an honor to know that we're here to serve a kind of dual purpose — playing historian as well as being the essential information source Cherokee Nation citizens and those in other tribes who visit our website or maybe subscribe to our newspaper," he said. "We are the source that provides them the information they need so that they are informed of what is going on and how it affects them as Cherokee Nation citizens."
Teri Saylor is a business writer in Raleigh, North Carolina. Contact her at terisaylor@hotmail.com.
Mullen Newspaper Company acquires 6 Kansas newspapers
Steve and Cynthia Haynes sold Nor'West Publishing/Haynes Newspapers on Dec. 1, 2022, forty-two years to the day after they purchased their first newspaper.
Carroll (Iowa) Times Herald sold, remains locally owned
The Tuesday, Nov. 29, edition of the Carroll (Iowa) Times Herald was the final newspaper published by the Wilson and Burns families, the three-generation local owners of the publication for 93 years.
Community Media Group acquires Burlington (Iowa) Hawk Eye
BURLINGTON, Iowa – The Burlington Hawk Eye has been acquired by family-owned Burlington Multimedia LLC, an affiliate company of Community Media Group (CMG) headquartered in West Frankfort, Illinois. The paper had been owned by Gannett Co. Inc.

redpajama_set_name: RedPajamaCommonCrawl


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Marbella Benahavís Estepona Manilva - La Duquesa Sotogrande
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Chef Renée Conrad, before opening "Il Ristorante", has been awarded a Michelin Star in 2005 beeing chef at Berlins "Facil" restaurant and 2006 beeing chef at the famous restaurant "Vivo" at Berlins Grand Hotel Esplanade.
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An exclusive sea-side resort with a privileged location, is set in breathtaking subtropical gardens, with a 300 meters beachfront with a sandy beach and three large swimming pools, and affords extraordinary views to the Mediterranean Sea, Rock of Gibraltar and African Coastline.
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Home // Ultimate Lifestyle Products // Automobiles // Bugatti Veyron 16.4
With its 16-cylinder four-wheel drive, the Bugatti Veyron 16.4 may well be the most sophisticated production vehicle of all times.
The Most Sophisticated Production Vehicle Of All Times
Boasting a maximum speed of more than 400 km per hour, the Veyron is unmatched in the super sports category. It offers a total of 1,001 HP, and its ample power reserves even at high speeds are the fabric of dreams for luxury-class limousines: for a constant speed of 250 km/h, the Veyron only needs 270-280 HP. This means that the seven-gear clutch transmission works with a torque of up to 1,250 Newton meters. The Electronic Stability Program (ESP) ensures the necessary flexibility and maneuverability at any speed. The Veyron reaches velocities that would literally lift the car off the ground – if it weren't for its ingenious aerodynamics, which keeps it firmly on the road even at full speed. Adjusting the back spoiler, reducing ground clearance, opening and closing the lids – it all adds to the perfect balance between propulsion and downforce. Such a super sports car may not seem to be brought to a halt easily, but the Veyron's ceramic brakes slow it down faster than it can accelerate. While it takes this exceptional car only 2.5 seconds to go from 0 to 100 km/h, it needs even less time – a mere 2.3 seconds – to come to a standstill from 100 (reference point). To reduce the risk of injuries in accidents, Bugatti had a Formula 1 safety concept adapted for the Veyron. All these technical details combine to make the Veyron a truly exceptional super sports car.
The car documents state a maximum velocity of 407 km/h, but that's an understatement. On April 19, 2005, inspection officials recorded a top speed average of 408.47 km/h. For years, the Bugatti engineers had worked diligently in order to push the 400 km/h boundary. No wind tunnel can simulate this velocity, which is why after each of a long series of improvements, the different ground clearance levels and the modifications of the rear fenders, spoiler and underbody were tested separately on high-speed test ranges. This ambition and diligence paid off, as the official speed measurement proves.
The Veyron's high velocity is due to the perfect combination of engine technology, consistent lightweight construction, specially developed tires, and the complex balance of propulsion and downforce. For not only the aerodynamic drag is a crucial factor at very high speeds, but also the precise adjustment of the downforce that holds the car to the road surface. And in addition to all this, the Veyron production vehicle meets the highest safety, reliability and maneuverability standards of even the most discerning drivers.
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Tooth enamel protects teeth by providing a hard surface resistant to wear and tear, withstanding impacts without breaking over the lifetime of an organism. The Giant Panda has particularly clever tooth enamel, according to researchers, which can recover its structure and geometry to counteract the early stages of damage [Liu et al., Acta Biomaterialia(2018), https://doi.org/10/1016/j.actbio.2018.09.053]. The team from the Institute of Metal Research, Chinese Academy of Science, the University of Science and Technology of China, Lanzhou University of Technology, and the University of California Berkeley believe their observations could be replicated in the tooth enamel of all vertebrates, including humans, and inspire the design of artificial durable ceramics.
"Tooth enamel possesses an exceptional durability and plays a critical role in the function of teeth, however, [it] exhibits a remarkably low resistance to the initiation of large-scale cracks comparable to geological minerals," points out Robert O. Ritchie, who led the study.
The ingenious design of the Panda's tooth enamel, which has to withstand a daily diet of bamboo – a material of remarkable strength and toughness, comprises parallel microscale prisms made up of vertically aligned nanoscale fibers of the mineral hydroxyapatite embedded in an organic-rich matrix. When there is an impact on the enamel, a variety of different deformation mechanisms take place to mitigate the growth of small cracks and prevent the formation of large cracks.
Hydration plays a key role in the process. The viscoeleasticity of the organic-rich matrix surrounding the mineral prisms and fibers facilitates self recovery, while the presence of water decreases the width of any cracks that do form, with only a minor cost in terms of hardness.
As the architecture of the Panda's tooth enamel is essentially similar to other vertebrates, the researchers believe that this self-recovery behavior is likely to occur in tooth enamel in general.
"Our findings also offer inspiration for the development of artificial durable, self-recoverable ceramic materials," says Ritchie.
The team is hoping to develop tooth enamel-inspired self-recoverable durable materials by introducing shape-memory polymers at the interfaces of ceramics.


International Space Station expedition lead Sunita Williams recently steered a Lego Mindstorms robot at an ESA facility in Darmstadt while she was orbiting overhead, proving that future space explorers could directly control a vehicle on a planetary surface while staying out of harm's way.
NASA and the European Space Agency (ESA) have successfully demonstrated an "interplanetary" communication network that one day may enable internet-like communications between space mission controllers and deep space spacecraft or robotic rovers on another planet.
U.S. astronaut Sunita Williams, commander of the International Space Station's Expedition 33 mission, used NASA's experimental Disruption Tolerant Networking (DTN) protocol to transmit two-way messages from a laptop to an ESA educational LEGO Mindstorms robot on Earth at the German European Space Operations Center in Darmstadt.
NASA's DTN architecture is a state-of-the art communications technology designed to enable standardized communications over long distances, taking into account time delays associated with deep space spacecraft and planetary robotic systems, agency officials said.
At the core of the DTN suite is something called the Bundle Protocol (BP), which allows standardized communications similar to the World Wide Web Internet Protocol (IP). The big difference between the two is that IP assumes a seamless end-to-end data path, while BP is built taking into account disconnections, errors and delays of signal — glitches that would be experienced in deep-space communications.
In due course the DTN technology could eventually become the cardinal technique of communicating between planets, as well as a way to operate deep space robotic rovers from Earth, the space agency said.
Work on DTN is part of NASA's Space Communication and Navigation Program, which coordinates multiple space communications networks and provides network support to regulate, maintain and grow the agency's space communications and navigation capabilities.
A working replica of the Curiosity Rover built with LEGO Mindstorm (Source: battlebricks.com).
LEGO Mindstorms is an educational construction kit used by universities and laboratories worldwide. It provides a programmable microcomputer and an array of actuators and sensors that can be assembled with traditional LEGO components, enabling rapid development and testing of full-featured autonomous robots. The kit is very popular among space enthusiasts, who constantly push it to the limits, studying new concepts or building replicas of existing ones, such as a working replica of the Mars Curiosity rover presented at the Build the Future in Space day at NASA's Kennedy Space Center.


Welcome to my review for the Simplicity Knitted Eternity Infinity Loop Neck Scarf I got to try in stright brown so it would match better with my coat but this photo shows how its is to be worn.
I love this scarf its thick and so very soft, I got the brown one in a single color but they have many to choose from. This is a great warm scarf and will be very welcome once we get the cold weather here . I was not prepared for how cold it got last year so I basically froze walking the dog .


A (9)-pack box of our hand-made popcorn balls in a variety of Caramel and Vanilla flavors; a fan favorite at Campbell's!
Grab this (9)-pack box of our delicious Popcorn Balls hand-made the old fashioned way using our signature copper scoops. We utilize our NON GMO popcorn seeds, pure cane sugars and real butter in every batch of these single-serving, roughly 4″ diameter popcorn balls. Grab some today and step back in time with this classic treat! Comes with a variety mix of (9) Caramel Popcorn Balls and Vanilla Popcorn balls!


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USDA Recalls
Mid-Michigan District Health Department realizes that timely information is critical to properly responding to a food recall. Whether you operate a licensed food establishment, or you are interested in food safety information to protect your family, you can access food recall information at the following links:
Michigan Department of Agriculture & Rural Development website maintains information regarding current active food recalls, archived recalls as well as links to FDA and USDA recalls at:
http://michigan.gov/mda/0,1607,7-125-1566_2404_2437---,00.html
The United States Department of Agriculture has recall information for foods containing meat, poultry and eggs at:
http://www.fsis.usda.gov/Fsis_Recalls/open_federal_cases/index.asp
The Food and Drug Administration website provides recall information for foods other than meat, poultry and eggs:
http://www.fda.gov/opacom/7alerts.html
Another good source of recall information for food can be found at:
www.recalls.gov
The following websites can offer food safety information for licensed food establishments, as well as the home kitchen:
http://www.foodsafety.gov/
http://www.fsis.usda.gov/PDF/Cooking_for_Groups.pdf
http://www.fightbac.org
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Organometallic Reagents
Organoboron
4-Cyanophenylboronic acid
Organoboron Aryls Nitriles Benzene Compounds
Formula : C7H6BNO2 Boiling Point : 355.9°C at 760 mmHg
[ 126747-14-6 ] Synthesis Path-Upstream 1~24
77% With copper(I) 3-metthylsalicylate; potassium carbonate In methanol at 65℃; for 3 h; General procedure: A dry flask was charged with the nitrogen containing heterocycles (1 mmol), aryl boronic acids (2.2 mmol), potassium carbonate (2 mmol) andCuMeSal (0.015 mmol)then anhydrous methanol (10 ml) was added. The reaction mixture was stirred at 65 oC, open to air, for 3 h (5 h in case of indole and benzimidazole), cooled to room temperature, filtered, and the precipitate was washed with methanol (2 ml), the filtrate was concentrated under vacuum, then stirred with ice water (30 ml) and extracted with ethyl acetate (3 × 50 ml), dried over sodium sulfate and the solvent was removed under reduced pressure. The residue was purified by chromatography or recrystallization as indicated with each compound.
52% With 4,4'-dimethyl-2,2'-bipyridines; oxygen; copper diacetate In water at 20℃; for 24 h; General procedure: Under an O2 atmosphere, a mixture of 4-methoxyphenylboroic acid (1a, 60.8 mg, 0.40 mmol), imidazole (2a, 13.6 mg, 0.20 mmol), Cu(OAc)2 (3.6 mg, 0.020 mmol), ligand I (3.7 mg, 0.020 mmol), and Triton X-100 (38.8 mg, 0.060 mmol) in H2O (4 mL) was stirred at room temperature for 24 h. The mixture was diluted with brine and extracted with AcOEt (30 mL.x.3). The organic layer was washed with H2O (10 mL.x.3) and dried over MgSO4. The solvent was removed under the reduced pressure and the residue was purified by SiO2 column chromatography using AcOEt to give N-(4-methoxyphenyl)imidazole (3aa) (23.0 mg, 66percent).
Reference: [1] ChemCatChem, 2016, vol. 8, # 18, p. 2953 - 2960
[2] Chemistry Letters, 2010, vol. 39, # 7, p. 764 - 765
[3] Synthetic Communications, 2015, vol. 45, # 2, p. 245 - 252
[4] Tetrahedron, 2012, vol. 68, # 38, p. 7794 - 7798
Reference: [1] Advanced Synthesis and Catalysis, 2015, vol. 357, # 14-15, p. 3104 - 3108
Reference: [1] Organic Letters, 2015, vol. 17, # 3, p. 476 - 479
Reference: [1] Angewandte Chemie - International Edition, 2014, vol. 53, # 39, p. 10510 - 10514[2] Angew. Chem., 2014, vol. 126, # 39, p. 10678 - 10682,5
53% With tetrakis(triphenylphosphine) palladium(0); 1,3-bis-(diphenylphosphino)propane; silver nitrate In acetone at 40℃; for 24 h; Autoclave; Inert atmosphere General procedure: The reaction was carried out in an autoclave containing a 10mL Teflon reaction tube. Pd(PPh3)4 (0.02 mmol), DPPP(0.04 mmol), and a magnetic stir bar were placed in the tubewhich was then capped with a stopper and flushed withargon. Then, aryl boronic acid (1 mmol), AgNO3 (1 mmol),and acetone (3 mL) were added to the tube. The tube was putinto the autoclave. Once sealed, the autoclave was purgedseveral times with CO, pressurized to 1 atm at r.t. and thenheated in an oil bath at 40 °C for 24 h. The autoclave wasthen cooled to r.t. and carefully vented to discharge CO in afume hood. Water (10 mL) was added, and the product wasextracted with CH2Cl2 (3 × 15 mL). The organic layers werewashed with brine, dried over Na2SO4, and evaporated. Thecrude product was purified by column chromatography onsilica gel using a mixture of EtOAc and PE as eluent to givethe products. The identity and purity of the product wasconfirmed by 1H NMR and 13C NMR spectroscopy and MSor HRMS spectrometry.
Reference: [1] Synlett, 2014, vol. 25, # 8, p. 1097 - 1100
[2] Chemistry - An Asian Journal, 2014, vol. 9, # 9, p. 2411 - 2414,4
Reference: [1] RSC Advances, 2014, vol. 4, # 83, p. 44312 - 44316
Stage #1: With n-butyllithium; 3 A molecular sieve In tetrahydrofuran; hexanes at -105 - -93℃; for 0.25 h;
Stage #2: With Trimethyl borate In tetrahydrofuran; hexanes at -105 - 20℃; for 2.43333 h;
Stage #3: With hydrogenchloride; water In tetrahydrofuran; hexanes A solution of 4-bromobenzonitrile (91 g, 0.50 mole) in THF (1.1 L) was dried in the presence of activated 3 molecular sieves at room temp. This solution was filtered and cooled to -100° C. A 1.6 M solution of n-butyllithium in hexanes (355 mL. 0.567 mol) was added to the cold solution over 15 min while maintaining the internal temperature between -105 and -93° C. To the resulting orange reaction mixture was added trimethylborate (81 g, 0.78 mol) over 3 min, briefly increasing the reaction temperature to -72° C. The reaction mixture was recooled to -100° C. over 5 minutes and then was allowed to warm slowly to room temperature over 2.3 h. The reaction mixture was acidified with 4N HCl to pH 2.2, and was diluted with CH2Cl2 (200 mL). The aqueous layer was separated and the organic layer was washed with brine (2.x.200 mL), dried over anhydrous MgSO4, filtered, and the solvent removed under reduced pressure to a pale yellow solid. This solid was additionally purified by dissolution in 1N NaOH and extraction into CH2Cl2/THF (1:1, 2.x.200 mL). The aqueous phase was acidified with 4N HCl to pH 2.2 and was extracted into CH2Cl2/THF (1:1, 500 mL). The combined organic extracts were concentrated to a crude solid (64.6 g) that was triturated with diethyl ether (160 mL) and dried under vacuum to afford the intermediate title compound (44.0 g, 59.9percent) as a white powder. 1H NMR (d6-acetone, 300 MHz): δ 8.03 (d, 2H, J=8.1), 7.75 (d, 2H, J=8.4), 7.54 (s, 2H).
Stage #1: With n-butyllithium In tetrahydrofuran; hexanes at -105 - -93℃; for 0.25 h;
Stage #3: With hydrogenchloride In tetrahydrofuran; hexanes; dichloromethane; water Preparation of 4-Cyanobenzene Boronic Acid
A solution of 4-bromobenzonitrile (91 g, 0.50 mole) in THF (1.1 L) was dried in the presence of activated 3 Å molecular sieves at room temp.
This solution was filtered and cooled to -100° C. A 1.6 M solution of n-butyllithium in hexanes (355 mL. 0.567 mol) was added to the cold solution over 15 min while maintaining the internal temperature between -105 and -93° C.
To the resulting orange reaction mixture was added trimethylborate (81 g, 0.78 mol) over 3 min, briefly increasing the reaction temperature to -72° C.
The reaction mixture was recooled to -100° C. over 5 minutes and then was allowed to warm slowly to room temperature over 2.3 h.
The reaction mixture was acidified with 4N HCl to pH 2.2, and was diluted with CH2Cl2 (200 mL).
The aqueous layer was separated and the organic layer was washed with brine (2*200 mL), dried over anhydrous MgSO4, filtered, and the solvent removed under reduced pressure to a pale yellow solid.
This solid was additionally purified by dissolution in 1N NaOH and extraction into CH2Cl2/THF (1:1, 2*200 mL).
The aqueous phase was acidified with 4N HCl to pH 2.2 and was extracted into CH2Cl2/THF (1:1, 500 mL).
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -105 - -93℃; for 0.25 h;
Stage #2: With Trimethyl borate In tetrahydrofuran; hexane at -100 - -72℃; for 0.133333 h; Preparation of 4-Cyanobenzeneboronic Acid.
Following a modified literature procedure of Perria, G. J.;et al., J. Am. Chem. Soc., 118, 10220-10227 (1996), a solution of 4-bromobenzonitrile (91 g, 0.50 mole) in THF (1.1 L) was dried in the presence of activated 3 Å molecular sieves at room temp.This solution was filtered and cooled to -100° C. Next, 1.6 M solution of n-butyllithium in hexanes (355 ML; 0.567 mol) was added to the cold solution over 15 min while maintaining the internal temperature between -105 and -93° C.
To the resulting orange reaction mixture trimethylborate (81 g, 0.78 mol) was added over 3 min, briefly increasing the reaction temperature to -72° C.
The reaction mixture was re-cooled to -100° C. over 5 min and then was allowed to warm slowly to room temperature over 2.3 h.The reaction mixture was acidified with 4N HCl to PH 2.2 and was diluted with CH2Cl2 (200 ML).The aqueous layer was separated and the organic layer was washed with brine (2-200 ML), dried (MgSO4), filtered, and reduced under pressure to give a pale yellow solid.This solid was additionally purified by dissolution in 1N NaOH and extraction into CH2Cl2/THF (1:1, 2-200 ML).The aqueous phase was acidified with 4N HCl to PH 2.2 and was extracted into CH2Cl2/THF (1:1, 500 ML).The combined organic extracts were concentrated to a crude solid (64.6 g) that was triturated with diethyl ether (160 ML) and dried under vacuum to afford the intermediate title compound (44.0 g, 59.9percent) as a white powder.
1H NMR (d6-acetone, 300 MHz): δ8.03 (d, 2H, J=8.1), 7.75 (d, 2H, J=8.4), 7.54 (s, 2H).
Reference: [1] Organic Letters, 2011, vol. 13, # 17, p. 4479 - 4481
[3] Dyes and Pigments, 2011, vol. 88, # 3, p. 274 - 279
[4] Patent: US2004/6114, 2004, A1, . Location in patent: Page 63
[5] Patent: US7034045, 2006, B1, . Location in patent: Page/Page column 37
[6] Patent: US2003/225266, 2003, A1, . Location in patent: Page 21
[7] European Journal of Organic Chemistry, 2003, # 15, p. 2829 - 2839
[8] Journal of Medicinal Chemistry, 2000, vol. 43, # 23, p. 4354 - 4358
[9] Journal of Organic Chemistry, 2002, vol. 67, # 15, p. 5394 - 5397
[10] Tetrahedron, 2004, vol. 60, # 25, p. 5373 - 5382
[11] Chemical Communications, 2010, vol. 46, # 15, p. 2677 - 2679
[12] Molecular Crystals and Liquid Crystals, 2010, vol. 518, p. 70 - 83
[13] Bulletin of the Korean Chemical Society, 2011, vol. 32, # 8, p. 2743 - 2750
[14] Chemistry - A European Journal, 2013, vol. 19, # 26, p. 8447 - 8456
[15] Journal of Organic Chemistry, 2013, vol. 78, # 13, p. 6427 - 6439
[16] Chemistry Letters, 2002, # 1, p. 60 - 61
Stage #1: With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; diisopropopylaminoborane; triethylamine; triphenylphosphine In tetrahydrofuran at 65℃; for 12 h; Inert atmosphere
Stage #2: With methanol In tetrahydrofuran at 0℃; Inert atmosphere General procedure: Triphenylphosphene (0.131 g, 0.5 mmol, 20 mol percent), p-iodoanisol (0.585 g, 2.5 mmol), and triethylamine (1.78 mL, 12.5 mmol) were added to a 50 mL round-bottomed flask equipped with a sidearm, condenser, and stir bar. This solution was then degassed by alternating vacuum and argon three times. Palladium dichloride (0.023 g, 0.13 mmol, 5 mol percent) was then added under positive argon pressure. After stirring at room temperature for 15 min, diisopropylaminoborane (5 mL, 1 M solution in THF, 5 mmol) was added and the reaction mixture was degassed again by alternating vacuum and argon three times. The reaction solution was then heated to reflux. After 12 h of reflux the reaction was cooled to 0 °C and 6 mL of methanol was added through the condenser slowly (Caution: exothermic reaction with evolution of hydrogen). After 15 min of stirring all the solvent was removed under reduced pressure to yield a black solid. This solid was dissolved with sodium hydroxide (3 M, 8 mL) and subsequently washed with hexanes (3.x.10 mL). The aqueous layer was then cooled to 0 °C (ice bath) and acidified to pH <=1 with concentrated HCl, with the boronic acid usually precipitating out as a white solid. The aqueous fraction was then extracted with diethyl ether (3.x.10 mL). The organic fractions were combined, dried with magnesium sulfate and filtered. The solvent was then removed under reduced pressure yielding a white solid.
Reference: [1] Tetrahedron, 2011, vol. 67, # 3, p. 576 - 583
Reference: [1] Organic Letters, 2007, vol. 9, # 9, p. 1711 - 1714
Reference: [1] Patent: US5130318, 1992, A,
[2] Organic Electronics: physics, materials, applications, 2014, vol. 15, # 11, p. 3316 - 3326
[3] Bioorganic and Medicinal Chemistry Letters, 2017, vol. 27, # 9, p. 1919 - 1922
25% With hydrogenchloride; n-butyllithium In tetrahydrofuran; hexane Preparation 42
A solution of 10.0 g (54.9 mmol) of 4-bromobenzonitrile in 100 mL of tetrahydrofuran was cooled to -85° C. wherupon 36.0 mL (57.6 mmol) of 1.6 M solution of n-butyllithium in hexane was added.
The mixture was stirred for five minutes and 19.0 mL (82.4 mmol) of triisopropylborate was added.
The mixture was stirred at -85° C. for 30 minutes then warmed to ambient temperature over one hour.
To the mixture was added 35 mL of 5 N hydrochloric acid and stirring was continued for 2.5 hours.
The mixture was diluted with 100 mL of saturated aqueous sodium chloride and extracted three times with 100 mL each of ethyl ether.
The combined organics were dried (MgSO4), filtered and concentrated in vacuo.
The residue was recrystallized from water and filtered to afford 2.0 g (25percent) of the title compound.
A solution of 10.0 g (54.9 mmol) of 4-bromobenzonitrile in 100 mL of tetrahydrofuran was cooled to -85° C. whereupon 36.0 mL (57.6 mmol) of 1.6 M solution of n-butyllithium in hexane was added.
Reference: [1] Journal of Medicinal Chemistry, 2004, vol. 47, # 23, p. 5612 - 5615
[2] Patent: US6303816, 2001, B1,
Reference: [1] Patent: US6576789, 2003, B1,
[2] Journal of Organic Chemistry, 2014, vol. 79, # 21, p. 10568 - 10580
Reference: [1] Bulletin of the Chemical Society of Japan, 1989, vol. 62, # 12, p. 3896 - 3901
Reference: [1] Journal of Organic Chemistry, 2009, vol. 74, # 19, p. 7364 - 7369
Reference: [1] Science China Chemistry, 2010, vol. 53, # 6, p. 1302 - 1315
[2] Journal of Thermal Analysis and Calorimetry, 2010, vol. 99, # 2, p. 391 - 397
[3] Chemistry - A European Journal, 2013, vol. 19, # 26, p. 8447 - 8456
Reference: [1] Journal of the American Chemical Society, 2016, vol. 138, # 9, p. 2985 - 2988
[2] Organic Process Research and Development, 2017, vol. 21, # 11, p. 1859 - 1863
Reference: [1] Chemistry Letters, 2002, # 1, p. 60 - 61
[2] Chemistry Letters, 2002, # 1, p. 60 - 61
Reference: [1] Journal of the American Chemical Society, 2012, vol. 134, # 28, p. 11667 - 11673
Reference: [1] Chemical Science, 2016, vol. 7, # 6, p. 3676 - 3680
Reference: [1] Patent: WO2014/8197, 2014, A1,
tetrakis[4-(4'-cyanophenyl)phenyl]ethene [ No CAS ]
Reference: [1]European Journal of Organic Chemistry,2003,p. 2829 - 2839
51% With potassium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 120℃; for 18.1667h; 3'-(hydroxymethyl)-5'-(trifluoromethyl)biphenyl-4-carbonitrile. A solution of [172023-97-1](3-bromo-5-(trifluoromethyl)phenyl)methanol (3.0 g, 11.8 mmol), 4-cyanophenyl boronic acid (5.2 g, 35 mmol), tetrakis(triphenylphosphine) palladium(0) (2.7 g, 2.4 mmol), and aqueous potassium hydroxide (41 mL, 1N, 41 mmol) in THF (80 mL) was degassed with nitrogen for 10 minutes and then heated at 120 C. for 18 hours. The reaction was cooled to ambient temperature and poured into water (100 mL), then was diluted with ethyl acetate (100 mL) and the layers were separated. The aqueous layer was extracted with ethyl acetate (2×20 mL) and the combined organic layers were dried with MgSO4 and evaporated. The residue was purified by chromatography on SiO2 with a gradient of ethyl acetate/hexanes of 5%-40%. The product 3'-(hydroxymethyl)-5'-(trifluoromethyl)biphenyl-4-carbonitrile (1.66 g, 51%) was obtained as a white solid. 1H-NMR (CDCl3, 400 MHz) delta 7.65-7.80 (m, 7H), 4.85 (s, 2H), 1.90 (bs, 1H). Mass spec.:278.2 (M+H).
Reference: [1]Patent: US2007/249607,2007,A1 .Location in patent: Page/Page column 58
77.5% With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In toluene; for 24h;Reflux; Inert atmosphere; Example 1 - Synthesis of 4,4'-(2l,7l-dibromo-9,9'-spirobi[fluorene]-2,7-diyl)dibenzonitrile (3); Step 1 - Synthesis of 4,41-(9,9'-spirobi[fluorene]-2,7-diyl)dibenzonitrile (2); To a mixture of [171408-84-7]2,7-dibromo-9,9'-spirobi[fluorene] (1 ) (1.76 g, 3.7 mmol) and 4- cyanophenylboronic acid (2.04 g, 13.9 mmol ), (PPh3)4Pd (0.23 g, 0.20 mmol) was added in a glovebox. Toluene (32 ml.) and 2M Na2CO3 (16 mL) was added into the mixture and heated to reflux with stirring in the dark for 24 h under the protection of nitrogen. After cooling to room temperature, the organic layer was separated and the aqueous layer was extracted with ethyl acetate (8OmL) twice. The combined organic layer was washed with water, brine and dried over sodium sulfate. The solvent was removed under reduced pressure and the crude product was purified by silica gel column chromatography with n- hexane/ethyl acetate (5:1 ) as eluent to give (2) as a white powder (1.94g, 77.5 percent). 1H NMR (CDCI3, 400 MHz, ppm) delta 7.98(d, 2H, J=8.0 Hz), 7.89 (d, 2H, J= 7.6 Hz ), 7.64 (dd, 2H, J= 1.6, 8.0 Hz), 7.60 (d, 4H, J= 8.4 Hz), 7.52 (d, 4H, J = 8.4Hz), 7.41 (t, 2H), 7.14(t, 2H), 6.94 (s, 2H), 6.80(d, 2H, J= 7.6 Hz).
Reference: [1]Journal of Polymer Science, Part A: Polymer Chemistry,2010,vol. 48,p. 292 - 301
[2]Patent: WO2011/8168,2011,A1 .Location in patent: Page/Page column 55-56
[3]Polymer,2010,vol. 51,p. 1270 - 1278
Reference: [1]Patent: WO2011/8168,2011,A1
80% With potassium phosphate; trans-diacetylpalladium(II) bis(dicyclohexylamine); In isopropyl alcohol; at 80℃; for 24h;Inert atmosphere; DAPCy (0.435 g, 0.6 mmol percent) and K3PO4 (6.3 g, 30 mmol) were added to a solution of 20 (3.88 g, 15 mmol) and p-cyanophenylboronic acid (2.64 g, 18 mmol) in deaireated iso-propanol (60 mL). The vigorously stirred mixture was warmed to 80 °C for 24 h under a nitrogen atmosphere. The solvent was concentrated under reduced pressure, the crystals which formed were filtered, dissolved in dichloromethane and passed through celite and evaporated under reduced pressure to give 21 (2.9 g, 80percent). Mp 204.4-205.4 °C.; 1H NMR (DMSO-d6, 300 MHz): delta 9.66 (s, 1H), 7.73 (d, 2H, J = 7.2 Hz), 7.57 (d, 2H, J = 7.2 Hz), 7.43 (d, 2H, J = 9.0 Hz), 5.77 (s, 2H). 13C NMR (DMSO-d6, 75 MHz) delta 145.9, 142.5, 133.7, 132.5, 130.6, 126.2, 125.0, 123.2, 119.9, 118.6, 109.1; HRMS (ESI): Calcd for C13H8N3O2 m/z: 238.0617 (M++1); Found m/z: 238.0612.
Reference: [1]Dyes and Pigments,2011,vol. 88,p. 274 - 279
[2]Dyes and Pigments,2012,vol. 92,p. 596 - 602
77% With copper(I) 3-metthylsalicylate; potassium carbonate; In methanol; at 65℃; for 3h; General procedure: A dry flask was charged with the nitrogen containing heterocycles (1 mmol), aryl boronic acids (2.2 mmol), potassium carbonate (2 mmol) andCuMeSal (0.015 mmol)then anhydrous methanol (10 ml) was added. The reaction mixture was stirred at 65 oC, open to air, for 3 h (5 h in case of indole and benzimidazole), cooled to room temperature, filtered, and the precipitate was washed with methanol (2 ml), the filtrate was concentrated under vacuum, then stirred with ice water (30 ml) and extracted with ethyl acetate (3 × 50 ml), dried over sodium sulfate and the solvent was removed under reduced pressure. The residue was purified by chromatography or recrystallization as indicated with each compound.
52% With 4,4'-dimethyl-2,2'-bipyridines; oxygen; copper diacetate; In water; at 20℃; under 760.051 Torr; for 24h; General procedure: Under an O2 atmosphere, a mixture of 4-methoxyphenylboroic acid (1a, 60.8 mg, 0.40 mmol), imidazole (2a, 13.6 mg, 0.20 mmol), Cu(OAc)2 (3.6 mg, 0.020 mmol), ligand I (3.7 mg, 0.020 mmol), and Triton X-100 (38.8 mg, 0.060 mmol) in H2O (4 mL) was stirred at room temperature for 24 h. The mixture was diluted with brine and extracted with AcOEt (30 mL.x.3). The organic layer was washed with H2O (10 mL.x.3) and dried over MgSO4. The solvent was removed under the reduced pressure and the residue was purified by SiO2 column chromatography using AcOEt to give N-(4-methoxyphenyl)imidazole (3aa) (23.0 mg, 66percent).
Reference: [1]ChemCatChem,2016,vol. 8,p. 2953 - 2960
[2]Chemistry Letters,2010,vol. 39,p. 764 - 765
[3]Synthetic Communications,2015,vol. 45,p. 245 - 252
[4]Tetrahedron,2012,vol. 68,p. 7794 - 7798
53% With nickel(II) iodide; trans-2-aminocyclohexanol hydrochloride; sodium hexamethyldisilazane; In isopropyl alcohol; at 75℃; for 15h;Inert atmosphere; 186 mg (0.594 mmol) of nickel(II) iodide, 90 mg (0.594 mmol) of trans-2-aminocyclohexanol hydrochloride and 3.63 g (19.8 mmol) of sodium hexamethyldisilazide were added to a solution of 2.91 g (19.8 mmol) of 4-cyanophenylboronic acid [M. Nishimura et al., Tetrahedron 2002, 58 (29), 5779-5788] in 20 ml of isopropanol. The suspension obtained in this way was stirred at RT under an argon atmosphere for 5 min. 2.1 g (9.90 mmol) of [25637-18-7]4-iodotetrahydropyran [Heuberger et al., J. Chem. Soc. 1952, 910] were then added. After the reaction mixture had been stirred at a temperature of 75° C. for 15 h, it was cooled to RT and largely freed from inorganic salts with methylene chloride by filtration over approx. 50 g of silica gel. The crude product was purified byMPLC (silica gel, mobile phase: methylene chloride). 986 mg (53percent of th.) of the title compound were obtained in this way.1H-NMR (400 MHz, CDCl3, delta/ppm): 7.60 (d, 2H), 7.32 (d, 2H), 4.12-4.07 (m, 2H), 3.56-3.50 (m, 2H), 2.87-2.79 (m, 1H), 1.86-1.73 (m, 4H).GC/MS (method K, EIpos): Rt=5.97 min, m/z=187 [M]+.
53% 186 mg (0.594 mmol) of nickel(II) iodide, 90 mg (0.594 mmol) of trans-2-aminocyclohexanol hydrochloride and 3.63 g (19.8 mmol) of sodium hexamethyldisilazide were added to a solution of 2.91 g (19.8 mmol) of 4-cyanophenylboronic acid [M. Nishimura et al., Tetrahedron 2002, 58 (29), 5779-5788] in 20 ml of isopropanol. The suspension thus obtained was stirred at RT under an argon atmosphere for 5 min. Then 2.1 g (9.90 mmol) of [25637-18-7]4-iodotetrahydropyran [Heuberger et al., J. Chem. Soc. 1952, 910] were added. After the reaction mixture had been stirred at a temperature of 75° C. for 15 h, it was cooled to RT and substantially freed of inorganic salts with dichloromethane by filtration through approx. 50 g of silica gel. The crude product was purified by MPLC (silica gel, eluent: dichloromethane). 986 mg (53percent of theory) of the title compound were obtained.1H NMR (400 MHz, CDCl3, delta/ppm): 7.60 (d, 2H), 7.32 (d, 2H), 4.12-4.07 (m, 2H), 3.56-3.50 (m, 2H), 2.87-2.79 (m, 1H), 1.86-1.73 (m, 4H).GC/MS (method 9, ESIpos): Rt=5.97 min, m/z=187 [M]+.
53% With nickel(II) iodide; sodium hexamethyldisilazane; (1S,2S)-2-hydroxycyclohexylamine hydrochloride; In isopropyl alcohol; at 20 - 75℃; for 15h;Inert atmosphere; Step 1: 4-(Tetrahydro-2H-pyran-4-yl)benzonitrile 186 mg (0.594 mmol) of nickel (II) iodide, 90 mg (0.594 mmol) of trans-2-aminocyclohexanol hydrochloride and 3.63 g (19.8 mmol) of sodium hexamethyldisilazide were added to a solution of 2.91 g (19.8 mmol) of 4-cyanophenylboronic acid [M. Nishimura et al., Tetrahedron 2002, 58 (29), 5779-5788] in 20 ml of isopropanol. The suspension obtained in this way was stirred at RT under an argon atmosphere for 5 min 2.1 g (9.90 mmol) of [25637-18-7]4-iodotetrahydropyran [Heuberger et al., J. Chem. Soc. 1952, 910] were then added. After the reaction mixture had been stirred at a temperature of 75° C. for 15 h, it was cooled to RT and largely freed from inorganic salts with methylene chloride by filtration over approx. 50 g of silica gel. The crude product was purified by MPLC (silica gel, mobile phase: methylene chloride). 986 mg (53percent of th.) of the title compound were obtained in this way. 1H-NMR (400 MHz, CDCl3, delta/ppm): 7.60 (d, 2H), 7.32 (d, 2H), 4.12-4.07 (m, 2H), 3.56-3.50 (m, 2H), 2.87-2.79 (m, 1H), 1.86-1.73 (m, 4H). GC/MS (method L, EIpos): Rt=5.97 min, m/z=187 [M]+.
[2]Patent: US2012/28950,2012,A1 .Location in patent: Page/Page column 16
[3]Patent: US2013/196964,2013,A1 .Location in patent: Paragraph 1148; 1149; 1150; 1151
4,4″-diamidino-5′-methoxy-m-terphenyl dihydrochloride [ No CAS ]
Reference: [1]Journal of Medicinal Chemistry,2013,vol. 56,p. 5473 - 5494
4-(pyridazin-3-yl)benzonitrile [ No CAS ]
Reference: [1]Organic Letters,2015,vol. 17,p. 5878 - 5881
C40H25N3 [ No CAS ]
Reference: [1]Journal of Materials Chemistry C,2015,vol. 3,p. 7345 - 7355
C17H18BN3 [ No CAS ]
Reference: [1]Journal of Organic Chemistry,2016,vol. 81,p. 969 - 980
[2]Journal of Organic Chemistry,2016,vol. 81,p. 969 - 980
4-(1,10-phenanthrolin-6-yl)benzonitrile [ No CAS ]
Reference: [1]Crystal Growth and Design,2016,vol. 16,p. 6992 - 6999
4-(4,5-dibromo-1-methyl-1H-imidazol-2-yl)benzonitrile [ No CAS ]
59% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 90℃; for 16h;Inert atmosphere; Step 2. 4-(4,5-Dibromo-l-methyl-lH-imidazol-2-yl)benzonitrile (0977) [00315] To a solution of 2,4,5-tribromo-l-methyl-lH-imidazole (3.94 g, 12.36 mmol), (4- cyanophenyl)boronic acid (1.816 g, 12.36 mmol) and potassium carbonate (3.42 g, 24.72 mmol) in dioxane (40 mL) and water (4 mL) was added tetrakis(triphenylphosphine)palladium(0) (0978) (0.714 g, 0.618 mmol). The mixture was degassed with nitrogen for 10 min, then heated to 90 (0979) °C for 16 h. After cooling to ambient temperature, EtOAc was added, the mixture washed with brine, dried over sodium sulfate, filtered and concentrated. Purification by silica gel chromatography (eluting with a gradient of 5-70percent EtOAc/hexanes) afforded 2.5 g (59percent) of 4- (4,5-dibromo-l -methyl- lH-imidazol -2 -yl)benzonitrile. 1H NMR (300 MHz, CDC13) delta 7.74 (m, 4H), 3.75 (s, 3H). MS (ESI) m/z 342.00 [M+H]+.
Reference: [1]Patent: WO2017/87837,2017,A1 .Location in patent: Paragraph 00315
(S)-1-(4-cyanophenyl)-6-oxopiperidin-2-carboxylic acid [ No CAS ]
With pyridine; oxygen; copper diacetate; triethylamine; In 1,2-dichloro-ethane; at 9℃; under 775.743 Torr; for 50h; (0582) Copper (II) acetate (7.61 g, 41.9 mmol) was added to a mixture of (S)-6-oxopiperidine-2- carboxylic acid (3.00 g, 21.0 mmol), (4-cyanophenyl) boronic acid (6.16 g, 41.9 mmol), pyridine (5.09 mL, 62.9 mmol) and triethylamine (8.76 mL, 62.9 mmol) in 1,2-dichloroethane (100 mL) at 9 °C. After the addition was complete, the mixture was stirred at 9 °C for 50 h under O2 (15 psi) protection. The mixture was concentrated under reduced pressure to give a reside, which was diluted with saturated sodium bicarbonate (300 mL), filtered with diatomaceous earth, and the filtrate was extracted with EtOAc (300 mL x 2), the aqueous layer was adjusted to pH 2 with 1N HCl, and then extracted with EtOAc (300 mL x 4). The collected organic layers were washed with brine (500 mL) and dried over anhydrous Na2SO4. The mixture was filtered and the filtrate was concentrated under reduced pressure to give the title compound as a solid. MS (ESI) m/z [M+H]+: 245.0.
Reference: [1]Patent: WO2017/222951,2017,A1 .Location in patent: Page/Page column 77
2'-(9H-carbazol-9-yl)-[1,10-biphenyl]-4-carbonitrile [ No CAS ]
3-isopropoxy-[1,1'-biphenyl]-4,4'-dicarbonitrile [ No CAS ]
3-methoxy-[1,1'-biphenyl]-4,4'-dicarbonitrile [ No CAS ]
4'-bromo-2'-ethyl-[1,1'-biphenyl]-4-carbonitrile [ No CAS ]
C13H8N2O3 [ No CAS ]
General procedure: A reaction mixture of (4-cyanophenyl)boronic acid 5 (150 mg,1.02 mmol, 1.0 equiv.), 4-bromo-2-chloro-6-methylphenol 6s (271 mg,1.22 mmol, 1.2 equiv.) and potassium carbonate (353 mg, 2.55 mmol,2.5 equiv.) in PEG400/H20 (4 mL/4 mL) was stirred at room temperaturefor 15 min, and then PdCl2 (1.8 mg, 0.01 mmol, 0.01 equiv.) wasadded to it. Stirring was continued for an additional 15 h until completeconsumption of starting material as judged by TLC. Then the reactionmixture was poured into water (20 mL) and extracted with ethyl acetate(10 mL * 4). The organic layers were washed with brine, dried overanhydrous Na2SO4, filtered and condensed. The residue was then purifiedvia flash chromatography on silica gel, eluting with EtOAc/petroleumethe to 7s as white solid in 54% yield.
Reference: [1]Bioorganic Chemistry,2019,vol. 89
4'-((2-((4-cyanophenyl)amino)thieno[3,2-d]pyrimidin-4-yl)oxy)-2'-nitro-[1,1'-biphenyl]-4-carbonitrile [ No CAS ]
C20H8F4N2 [ No CAS ]
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); In water; toluene; at 100℃; for 12h; Unitine , 4 -bromotetrafluorobenzene, 0.11 muM 1 unitunitunito-cyanophenylboronic acid 0.1 muM 4 - 0 . 001molPd under a nitrogen atmosphere2(Dba)3Unitunitunits, 0.002 muM s-phos, 0 . 2molK3PO4The unitz reacted 300 ml 12h. 100 ml was found in a mixed solution consisting of unit_transformants '-type 100 C'-type '.'. Obtained M1
Nitriles
(5-Cyano-2-methylphenyl)boronic acid
3-Cyano-2-methylphenylboronic acid
Aryls


text:
@interface HLServiceHttpProxy ()

// httpDispatcher
//HttpDispatcher* _httpDispatcher;
@property (nonatomic, retain) HLHttpDispatcher* httpDispatcher;
//@synthesize httpDispatcher = _httpDispatcher;

// responseHandler
//BrokerMessageResponseHandler* _responseHandler;
@property (nonatomic, retain) HLBrokerMessageResponseHandler* responseHandler;
//@synthesize responseHandler = _responseHandler;

@end

////////////////////////////////////////////////////////////////////////////////
////////////////////////////////////////////////////////////////////////////////
////////////////////////////////////////////////////////////////////////////////
#pragma mark -

@implementation HLServiceHttpProxy

-(HLBrokerMessage*)process:(HLBrokerMessage*)request {

    CAJsonArray* messageComponents = [request toJsonArray];
    NSData* bodyData = [CAJsonArrayHelper toData:messageComponents];

    id<HLEntity> entity = [[HLDataEntity alloc] initWithData:bodyData];

    NSString* requestUri;

    if( nil == _authenticator ) {
        requestUri = @"/_dynamic_/open/services";
    } else {
        if( [_authenticator authInt] ) {
            requestUri = @"/_dynamic_/auth-int/services";
        } else {
            requestUri = @"/_dynamic_/auth/services";
        }
    }

    HLHttpRequestAdapter* requestAdapter = [[HLHttpRequestAdapter alloc] initWithRequestUri:requestUri];
    [requestAdapter setRequestEntity:entity];

    [_httpDispatcher post:requestAdapter authenticator:_authenticator responseHandler:_responseHandler];

    return [_responseHandler getResponse];

}

// can return nil
-(NSString*)realm {

    if( nil == _authenticator ) {
        return nil;
    }

    NSString* realm = [_authenticator realm];
    return realm;

}

-(NSString*)serviceName {
    return nil;
}

#pragma mark instance lifecycle

-(id)initWithHttpDispatcher:(HLHttpDispatcher*)httpDispatcher {

    HLServiceHttpProxy* answer = [super init];

    [answer setHttpDispatcher:httpDispatcher];
    answer->_authenticator = nil; // just to be clear about our intent
    answer->_responseHandler = [[HLBrokerMessageResponseHandler alloc] init];

    return answer;

}

-(id)initWithHttpDispatcher:(HLHttpDispatcher*)httpDispatcher authenticator:(HLAuthenticator*)authenticator {

    HLServiceHttpProxy* answer = [super init];

    [answer setHttpDispatcher:httpDispatcher];
    [answer setAuthenticator:authenticator];
    answer->_responseHandler = [[HLBrokerMessageResponseHandler alloc] init];

    return answer;

}

-(void)dealloc {

	[self setHttpDispatcher:nil];
	[self setAuthenticator:nil];
    [self setResponseHandler:nil];

}

#pragma mark fields

// httpDispatcher
//HttpDispatcher* _httpDispatcher;
//@property (nonatomic, retain) HttpDispatcher* httpDispatcher;
@synthesize httpDispatcher = _httpDispatcher;

// authenticator
//Authenticator* _authenticator;
//@property (nonatomic, retain) Authenticator* authenticator;
@synthesize authenticator = _authenticator;

// responseHandler
//BrokerMessageResponseHandler* _responseHandler;
//@property (nonatomic, retain) BrokerMessageResponseHandler* responseHandler;
@synthesize responseHandler = _responseHandler;

@end

redpajama_set_name: RedPajamaGithub


text:
FHO RACING SET TO SPEARHEAD BMW'S 2022 ROAD RACING CAMPAIGN WITH HICKMAN AND MCCORMACK
FHO Racing will make their much-anticipated debut at the International road races in 2022, lining up as the official BMW Motorrad road racing team with Peter Hickman and Brian McCormack on board the Bavarian-built machines.
Both multiple road race winner Hickman and McCormack will ride BMW M 1000RR machinery for Faye Ho's team in the Superbike and Superstock categories at the Isle of Man TT and North West 200 as well as the Ulster Grand Prix, should it make its return to the road racing calendar.
Both riders will also contest the Macau Grand Prix, which is set to return in November next year, with all four events having failed to run since 2019 as a result of the COVID-19 pandemic.
Hickman will be aiming to carry on from where he left off in 2019, a year that saw him take Superbike and Superstock success at the world-famous Isle of Man TT. He remains the outright lap record holder around the Mountain Course, his lap of 135.452mph set on the BMW S 1000 RR in 2018.
2019 also saw him win Superbike and Superstock races at the Ulster Grand Prix, where he set a new outright lap record of 136.415mph. The lap saw him and BMW enter the Guinness Book of Records with their lap being a new world record for a circuit still in use.
The Louth-based rider was also victorious in the Superstock class at the North West 200 whilst second place was taken at the Macau Grand Prix, a circuit where he's already won on three occasions whilst riding BMW machinery.
McCormack, meanwhile, continues with the team after having a solid BSB season in 2021, a campaign which saw him get valuable track time ahead of the return of the International road races next year.
Hailing from Waterford, McCormack is the fastest rider from Southern Ireland ever at the Isle of Man TT with his lap of 128.812mph in the 2019 Senior TT helping him achieve his best finish on the island of ninth. He'll be aiming to improve upon that next year and also break the 130mph barrier for the first time.
In addition, McCormack has a best finish of fifth at the Ulster Grand Prix, recorded in 2018, on his impressive CV as well as a host of other top ten finishes around the high-speed Dundrod circuit. Joining FHO Racing for 2022, when he'll continue to receive support from the Roadhouse Bar in Macau, gives him a perfect opportunity to make a real impression on the International road race results, something which he aims to grab firmly with both hands.
Faye Ho, Team Owner: "It's a real honour for FHO Racing to be chosen by BMW Motorrad as their official team at the 2022 International road races especially as we've only been in existence for a year! It shows the progress and impression we've made, both on and off the track, and returning to the roads in 2022 with Peter and Brian is very exciting for everyone connected with the team."
"Peter's record speaks for itself whilst Brian's results have continually improved and we're quietly confident both riders will excel next season. On a personal note, the road races are very important to me and having attended the likes of the TT and, obviously, Macau on a regular basis, I'm thrilled to be attending them in 2022 with the team and in an official capacity."
Hickman said: "After three years away, I'm delighted to be heading back to the International road races next year and equally delighted to be doing so with FHO Racing. Having re-signed with the team in the British Championship, after a successful season this year, it's great to be contesting the likes of the TT and NW200 with them too and I can't wait.
"I had some great times at the road races with the S 1000RR and with the way it performed on the short circuits this year, I'm excited to see what we can do with the M 1000RR on the roads; I'm confident we'll turn a few heads!"
McCormack said: "To say I'm over the moon to be riding the FHO Racing by Roadhouse Macau BMW for Faye and the team alongside Hicky at the International roads and selected National Superstock rounds would be an understatement! The team are amazing and although this year was challenging for me with injuries and learning everything that goes with riding a Superbike, everyone made me feel at home and looked after me really well.
"Riding for the team in 2022 will give me the best tools and team I need to move up the results at the Isle of Man TT, North West 200, Macau GP and, hopefully, the Ulster GP too. I can't thank Faye, Darren, Hicky and rest of the team enough for this chance. I am also delighted to continue with the backing from Roadhouse Macau for next season."
Scott Grimsdall, BMW Motorrad UK, Head of Marketing and PR said: "We're absolutely delighted to be returning to the international road racing programme following the challenges of the last few years, and it's great to be doing so with FHO Racing. The Isle of Man TT and North West 200 have been an integral part of BMW's racing calendar especially in the last decade and we firmly believe we can add to the considerable success we've already achieved next year.
"In a short space of time, the FHO Racing team have more than proved themselves and with Peter Hickman spearheading BMW's road racing challenge in 2022, it's a really exciting prospect for us. We can't wait for the racing to start!"


Clean cosmetics just entered another dimension, and the brand leading the way is Āether Beauty, an emerging color cosmetics line offering highly pigmented eye shadow palettes made with zero-waste materials (read: no magnets or mirrors). Effective immediately: clean, sustainable beauty is on the same plane as traditional beauty brands. When it comes to beauty and packaging innovation, Āether is leaps and bounds ahead of the rest – appealing to consumer tastes and values, without compromise. The Āether Eye Shadow palette is considered a zero-waste product, which means each component is recyclable or reusable. The palette contains no mirror or magnets which would pose a problem for recycling centers, just a small price to pay for sustainability. And, as you'll read, Āether ticks all the boxes of a blue beauty brand: by sourcing ethically and giving back to the environment.
We wanted to know the magic behind this unicorn cosmetics brand, so we tracked down Tiila Abbitt, a traditional beauty executive-turned-indie-entrepreneur who saw a big opportunity to create a way to bring real, clean, smart beauty to both the planet and the consumer. Meet the woman behind a brand that's just getting started, leading the way in zero-waste beauty.
When did you come up with the idea to launch Āether Beauty, a zero-waste makeup brand? Can you give us a glimpse into your thought and development process?
I have been a vegetarian since I was 14 years old and have always lived this organic lifestyle. I started to have a disconnect working at Sephora, when we were formulating conventional beauty, so I volunteered and became the Head of R+ D for Sustainability for the entire retailer. I started to notice that all the clean and natural color brands just did not compete when it came to efficacy of conventional beauty products. Not only that, but the space was a bit boring to me. There was no fun, no trends and no storytelling beyond messaging 'clean and nontoxic.' I could see a huge hole in the market for a clean brand that could stand up next to the conventional brands at Sephora. So, I decided to leave and create my own brand, Āether Beauty to fill that whole. Vegan, cruelty-free and clean ingredients were the baseline for me. I wanted to take the same approach with making sure ingredients were also organic, fair trade and sustainably sourced. As I'm a packaging developer as well, I thought it was so strange that in this space there weren't brands that were truly 100% recyclable. The EPA just reported that on third of landfill waste was mad of personal care products, and I didn't want to launch a brand that would end up in a landfill. I wanted to put as much attention to packaging as I did to the formula.
At Beauty Heroes we believe in supporting the growth of Blue Beauty, the movement to create products that are light on the environment while giving back to it. Do you give back to environmental causes? What else makes Āether a Blue Beauty Brand?
Yes, I wanted the brand to also be a vehicle for philanthropy! I could not decide on just one company to donate proceeds to, so I've paired up with a different charity for each product. For the Rose Quartz Crystal Gemstone Palette, with rose quartz being a water stone, I partnered with The Water Project, which provides clean water to communities in Africa. With the Crystal Grid Palette, I partnered with The Rainforest Foundation, which helps secure land rights to indigenous people in the rainforest. I am also open to hearing from clients for charity suggestions and there's a space on my website for clients to do so.
Do you think living in San Francisco influenced your path to creating a zero-waste makeup line?
No. I've lived here more than 15 years but had this mentality prior to moving here. I do appreciate that the city has mandatory composting and I've learned a lot since moving here, but it wasn't necessarily coming from this city. I think San Francisco lets anyone be who they are, which I have always appreciated, but actually it's a pretty hard place to be vegan, surprisingly. You can actually get more vegan options in Vegas of all places than in San Francisco.
Can you tell us exactly how you recommend recycling and composting the components of the eye shadow palettes, making the zero-waste?
Yes, you need to pop the aluminum pans out, which are easily removed with a tweezer or something you can leverage. Then you simply recycle the pans separately from the paper palette and cut the elastic off, which you can reuse as a hair tie. I'm always losing my hair ties too!
You've made sure your eye shadow formulas are clean, yet with a lot of pigment and wide shade range. Can you share some of the challenges and insights into the formulas, and what makes the shadows so long-wearing and beautiful?
Actually, since I was in charge of product development for Sephora for makeup collaborations for over seven years, the formulation was always the easy part. I like to say that I received my second master's degree at Sephora from some of the smartest and amazing women in the beauty industry. Sephora taught me exactly how to push formulas, how to substitute ingredients, and what the client is truly looking for. We used to constantly stalk the ratings and reviews because clients don't hold back when they don't like a product. Plus I had the macro lens to see what was trending and working across all brands, not just working on my own so it gave me an entire overview of the category and that helps you ideate brand new ideas as well. As far as ingredients, what many people don't know is that 25% of the world's mica unfortunately comes directly from child labour. Along with the rise in natural and clean beauty, people are straying away from talc and using mica instead as a base of any powder formula and unfortunately contributing to this problem. If I cannot vet the source of my mica, I actually substitute synthetic mica, which is exactly how it sounds: made in a lab. However, natural mica grows in the ground with other minerals and tends to be all smokey and gray in color, while if you create it in a lab, it's clear. So when you formulate with it, you get purer shades and a totally different shade range. It's also rated a 1 on the EWG, so it's nontoxic but also more expensive than natural mica. Understanding tricks like this helps me push to get shades never before seen in this clean beauty space.
What's next for Āether Beauty?
Being a product developer, I have about two years of product that I have been developing, including other innovations in new formulas as well as innovations in packaging. I can't wait for everyone to see what I have been working on!
TOPICS: All, Behind The Scenes, Ingredient Intel, Project Blue Beauty, Use Less. Love More.


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I-280 freeway in San Francisco closed after freeway shooting
Southbound I-280 at Alemany Boulevard was closed because of a shooting. Jan. 15, 2018
A portion of Interstate 280 in San Francisco was closed early Monday because of a freeway shooting.
Southbound at Alemany Boulevard at Mission Street was just just after 3 a.m.
California Highway Patrol Officer Francisco Garcia said there were between three to six victims, who drove themselves to San Francisco General Hospital.
The freeway opened about 7 a.m.


An Apple a Day, But Where Can I Find the Apples?
Hello. My name is Dr. Michael Aaronson, MD, I'm a kidney doctor. I specialize in kidney problems and high blood pressure. It's a pleasure to be part of the CHI Health family. To read more about me (and CHI Health Nephrology), please feel free to check out my bio page. I am looking forward to providing high quality content in multiple formats including MP3 and video on YouTube. I encourage you all to participate, weighing in at your convenience. So let's get started!
I truly appreciate Dr. Van De Graaff's position on generic medications. His points are well taken. However, sometimes the generic co-pays can add up to be prohibitively expensive. So what can we do about that?
One option to consider to help you navigate through the quagmire of options is to utilize a service here in Omaha, Nebraska. The service is called Volunteers Assisting Seniors (VAS). They do legal services, conservators, homestead exemption, and most importantly for the purpose of this discussion: The Nebraska Senior Health Insurance and Information Program (SHIP). The SHIP program specializes in Medicare. It helps seniors enroll in an appropriate plan that fits the person's needs. I like this program because it offers a non-biased approach to help you get the medications and services that you need.
Now, once you have access to the meds, your next step is to remember to take your medication. If you don't take it, it can't help you.
Here is an example of an approach to consider: Fall is approaching … a 65 year old who has had a heart stent placed and needs significant cholesterol reduction requiring a branded product has just run out of money and is in the donut hole. He can't afford his medication. What can he do?
He can stop taking his medication. Or, he can consider samples – if available. Perhaps switching to a less expensive generic for 2 months – then restarting his original prescription in January – is an option. Maybe he should call VAS to make sure he is in the right plan.
Do you have any other ideas on how we can help this patient? Please comment below.
So think ahead, utilize available services, and stay healthy!


The Mombasa Boyfriend Sweater Remix stays true to the casual elegance of its original. Again we see a bold, graphic print contrasted against a sporty black crepe fabric. Pair it with the Mombasa Remix Pants for a bold look. Made in South Africa with local fabric.


LOS ANGELES (AP) - The powerful earthquake that struck beneath the Gulf of Alaska generated a tsunami, but before gauges could show that it was very small, warnings went out to a vast swath of the state, British Columbia and the West Coast.
Analysis by the National Tsunami Warning Center allowed experts to downgrade and call off all alerts in less than four hours. But an official involved in the process says the protocol for the immediate warning only considered magnitude and location.
David Hale, a lead decision maker with the center, says that's because there's not enough time to determine whether or not a wave has been created before alerting the closest people.
By the time the final advisory was canceled, the largest observed tsunami height was less than a foot.


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Network Rail
McNicholas Construction
A key part of maintaining the running of a railway network is train maintenance. Network Rail is responsible for maintaining the 20,000 miles of track across the UK. In order to do this, they have a fleet of engineering trains which they use to maintain the tracks.
Network Rail's engineering trains needed a space for their own repairs to ensure maximum performance, in a safe area to protect the engineers from other trains and the elements. Secure train sheds were created for this task; enclosed spaces providing access to all areas of the train for engineers to perform the necessary maintenance and refurbishments.
HAG was asked to replace the shutters on the train sheds to ensure safe, secure and easy access to the building for trains, equipment and engineers.
To achieve this, we selected 2 of our products; the Armourguard F1 and our horizontal sliding C door. The F1 was selected because, as an insulated roller shutter, it provides sound and heat insulation from the outside while also maintaining the necessary security. We chose to use a sliding C door for the project as it provides secure but easy access for those trains requiring repair. The end result was a sheltered train shed, designed for both the safety of the engineer and easy access for ongoing train repair and refurbishment.


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Who was the future GM? Fabiano Caruana, Italy's top grandmaster!
10/18/2007 – He was born in Miami, Florida, in 1992, went to school in Brooklyn, played in Queens in the Susan Polgar Club, trained with Pal Benko, defeated a GM at the age of ten, moved to Spain, then to Hungary, and made his GM norms at the age of 14 years. Today, at 15, he is the strongest player in Italy and the world's youngest grandmaster. Pictorial answer to our quiz.
On this DVD you will be taken on a journey through what is arguably the sharpest opening line known to men.
The answer to our quiz last week – the one with the sepia picture of a child destined to become a grandmaster and the strongest player of his country – was not Yasser Seirawan, Nick de Firmian, Boris Gelfand, Alexei Shirov, Nigel Short or one of the dozen or so other names suggested by our readers.
The correct answer is Fabiano Caruana, currently fifteen years old, the youngest grandmaster in the world and strongest player in Italy, the country of his parents and the one he represents.
With and without out the Photoshopped sepia tones: Fabiano in 1995, aged three, in Miami, Florida
Astonishingly in spite of our carefully crafted misleading clues (all perfectly true, of course) almost 50% of our readers got it right. Many recognised the eyes, many remembered a recent ChessBase article and interview. Some used the board position we provided to search for the original gamescore and identify the player (yes, Virginia, there are such people). And some used simple logical deduction, like Robert Bernard of Glen Ridge, NJ USA, who wrote: "It was a cute idea to put the sepia tone on the picture of Fabiano Caruana, but the fact that he's wearing an obviously plastic hat, gives away the the photograph is really not that old!" You simply can't fool all of the people all of the time.
Fabiano Caruana – youngest US and Italian GM in history
Fabiano Caruana was born in Miami, Florida on the 30th of July, 1992, and is solely of Italian ancestry, since all eight of his great grandparents originate from Italy. Fabiano also has dual citizenship – currently he holds passports from both the United States and Italy.
At the age of four the family moved from Miami to Park Slope Brooklyn (Bobby Fischer's former neighborhood). There, at the age of five, in an after school program at Temple Beth Elohim, his chess journey began. Within six months he played his first tournament at Susan Polgar's club in Queens, New York. Susan's club helped start his chess career. Later he played at many clubs within the New York City area. Fabiano's trainers were National Master Bruce Pandolfini and GM Miron Sher. He also trained with GM Pal Benko, when Pal was spending summers in New Jersey, and via the Internet with GM Gregory Kaidanov.
One of the earliest pictures: Fabiano at two in the home garden at Coconut Grove, Florida
The future grandmaster and top Italian player at three
By the age of twelve Fabiano was a FIDE Master, having won two gold medals and one silver medal at the Pan-American Youth Championships, and also multiple national scholastic championships. He also set the record – at the age of ten – of the youngest ever American to defeat a grandmaster in a USCF sanctioned tournament, surpassing the record previously held by GM Hikaru Nakamura.
Fabiano with his mom on his third birthday in 1995
With his dad in their Coconut Grove home in Florida
In his nursery class at Temple Beth Am in Miami, Florida
At age 4: first grade school photo at Park Slope, Brooklyn
Having decided to pursue chess professionally, it was time to move forward, and Europe was the place to be.
So, in November of 2004 the family moved from Brooklyn to Madrid. This ended his early chess years in the United States.
Madrid was selected solely because IM Boris Zlotnik lived there. Fabiano trained with Boris from November of 2004 to Marrch of 2007, and Boris' training and constant detailed attention helped him tremendously. His Elo increased from 2219 to 2513, and he earned an IM title along with his first GM norm.
The eleven-year-old playing at the Marshall Chess Club against IM Yury Lapshun
In April of 2007, it was time to again move forward, and the family moved to Budapest to start training with GM Alex Chernin. Fabiano's second GM norm came in that same month (April), while playing at the First Saturday tournament and sleeping on the floor of an empty flat in the Buda hills. In July 2008 he completed his third GM norm, setting the record as the youngest ever American and Italian to earn the GM title, again surpassing the record set by GM Hikaru Nakamura.
Regarding federations: from age five to age 13 Fabiano played for the United States. But in October of 2005 he changed his FIDE affiliation to Italy. This was a natural change since he lived in Europe and intended to stay there. In the foreseeable future the family intends to move to Italy.
Fabiano's relationship with the Italian Chess federation continues to be excellent. He is now the highest ranked player in Italy, and the Italian federation supports his efforts 100%. But, he says, "although my FIDE affiliation is with Italy, I am still a member of the United States Chess Federation, and I greatly value my good relationship with the United States Chess Federation."
There comes a time in a boy's life when he starts giving simultaneous exhibitions
"My situation with regard to choice of federations is somewhat unique," he continues. "Due to my dual citizenship, I can play for Italy or the United States, and due to my residency, I can play for Hungary. It's nice to have choices." However, his first priority is to benefit Italian chess by raising its visibility in Italy, such that the Italian National Olympic Committee (CONI) takes notice and upgrades its official status from an "Associate Sport" to a "National Sport" such as football, tennis, etc. This change would provide for full financial backing of chess at the national level.
Regarding sponsorship, Fabiano says that his sponsorship in the United States understandably ended when I moved to Europe. "My sponsor will always be one of the most memorable people in my life," he adds. Now that he is a highly recognizable young GM playing for Italy he can anticipate that an Italian (hopefully corporate) sponsor will come forward.
At 14 Fabiano is celebrated as a GM, Italian Champion and the country's top ranked player
Fabiano does not attend school, but studies at home, and his academics, although not formal, are very solid. He enjoys reading, writing, movies, and ping pong. For physical conditioning he runs ten kilometers every day, when not playing in a chess tournament.
For the coming year of 2008 Fabiano's preliminary tournament plans include Corus, the European Individual Championship and the Mitropa Cup. "I especially look forward to the 2008 Olympiad in Dresden," he says.
Youngest grandmasters in history
Sergey Karjakin
Parimarjan Negi IND 13 3 22 2006
Bu Xiangzhi
Teimour Radjabov
Ruslan Ponomaryov
Maxime Vachier-Lagrave
Peter Leko
Yuri Kuzubov
Nguyen Ngoc Truong Son
Koneru Humpy
Pentala Harikrishna
Alejandro Ramirez
Previous ChessBase reports
Choosing the best in the US by Susan Grumer
Fabulous Fabiano (Fabiano defeated GM Aleksander Wojtkiewicz in 2002)
Chess Prodigies and Mini-Grandmasters


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when new Calgary Flames events are added in your area.
About Calgary Flames Tickets
The Flames organization started out in Atlanta. The short-lived Atlanta Flames played from 1972 to 1979 before the team relocated to Calgary for the 1980-81 season. The Flames swapped out their flaming A logo for a flaming C, but the old Atlanta Flames logo has remained in use as the "A" on the jerseys of Calgary's alternate captains.
Shortly after they arrived in Calgary, the Flames developed a contentious rivalry with the Edmonton Oilers. The Oilers teams of the 1980s were some of the most talented the NHL has ever seen, but the Flames always managed to be one of their toughest opponents, particularly in the playoffs. In the 1986 Stanley Cup Playoffs, the Flames defeated the Oilers in the Division Finals when, with Game 7 tied at 2, Oilers' defenseman Steve Smith accidentally played the puck off his own goalie and into Edmonton's net. Smith's own-goal won the series for Calgary, and the Flames ultimately advanced to their first Stanley Cup Final. It took the Flames until 1989 to win their first Stanley Cup, and they did so with a stacked roster that included Theoren Fleury, Gary Roberts, Joe Mullen Doug Gilmour, Lanny McDonald, Al MacInnis, and Joe Nieuwendyk. The Flames defeated the Montreal Canadiens in six games.
After many disappointing seasons in which the Flames failed to qualify for the playoffs, the team made a surprising run to the 2004 Stanley Cup Final. Led by the goal scoring of Captain Jarome Iginla and stellar goaltending from Miikka Kiprusoff, the Flames defeated some of the Western Conference's toughest teams but lost the Stanley Cup to the Lightning after seven games. Iginla and Kiprusoff helped the Flames make the playoffs in four consecutive seasons after their run to the Final.
After Kiprusoff's retirement and Iginla's departure, the Flames developed exciting players like Johnny Gaudreau and Sean Monahan.
Frequently Asked Questions About Calgary Flames Tickets
How much are Calgary Flames tickets?
Flames ticket prices on the secondary market can vary depending on a number of factors. Typically, Flames tickets can be found for as low as $10.00, with an average price of $65.00.
How to get cheap Flames tickets?
If you're looking for cheap Flames tickets, tickets can be found for as low as $10.00. Additionally, once you click on your preferred event date, use the "sort by price" button located in the top left hand corner of the event page to sort all available Flames tickets by cheapest tickets available.
Where do Calgary Flames play?
The Flames home games are played at Scotiabank Saddledome in Calgary, Canada.
What teams are in the Calgary Flames division?
The Flames are in the Pacific division with the Anaheim Ducks, Arizona Coyotes, Edmonton Oilers, Los Angeles Kings, San Jose Sharks, Vancouver Canucks, and Vegas Golden Knights.
Do I need to print my Flames tickets?
Print-at-home tickets are no longer an option for NHL games. Calgary Flames are exclusively using mobile ticket entry to all games.
Does my child need a ticket for Flames games?
Each NHL team has their own child ticket policy. Some teams have age requirements and others have restrictions on height. The Flames policy states all children under 2 are free.
How to buy Calgary Flames tickets
SeatGeek is the best way to browse, find, and buy Flames tickets.
Browse the above listings of Flames tickets to find a show you would like to attend. Once you find the perfect date and show time, click on the button on the right hand side of the event to see all available tickets for that show.
Next, explore all available Flames tickets on the left hand side of the screen. Filters at the top of the page allow tickets to be sorted by price, or by SeatGeek's Deal Score feature, which ranks tickets by value and tells you exactly how good of a deal you're looking at. On the right hand side, you can explore SeatGeek's interactive maps to find the perfect seating section, and to get a preview of what a view from a seat in that section will look like.
To buy Flames tickets, click the ticket listing and you will be directed to SeatGeek's checkout process to complete the information fields.
SeatGeek will process your order and deliver your Flames tickets.
Calgary Flames Ticket Prices
The Hottest Matchups in the NHL Season
It may be the middle of the summer, but that doesn't mean the NHL news cycle slows down, as both the schedule release and free agency have occurred since the last newsletter. With the schedule locked ...
Calgary Flames Top Matchups
Flames vs. Oilers
Flames vs. Maple Leafs
Flames vs. Rangers
Flames vs. Bruins
Flames vs. Canucks
Flames vs. Canadiens
Flames vs. Lightning
Flames vs. Blackhawks
Flames vs. Jets
Flames vs. Capitals


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18 Yellow Roses ~ Bobby Darin
Robert Silvestri
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In 1962, Darin began to write and sing country music, with hit songs including "Things" (US #3/UK #2) (1962), "You're the Reason I'm Living" (US #3), and "18 Yellow Roses" (US #10). The latter two were recorded by Capitol Records, which he joined in 1962, before returning to Atlantic four years later.
Darin wrote this song for the mother of actress Sandra Dee. Darin met Dee in 1960 when they were shooting a movie together in Portofino, Italy, called Come September. Darin was smitten, and decided it was best to get in her mother's good graces. Every day of the 4 week shoot, he sent Dee's mother 18 yellow roses - this was portrayed in the movie Beyond The Sea with Darin saying, "You always make sure the mama dog likes you before you go near her puppy." Darin and Sandra Dee eloped later that year, and were married until 1967. (thanks, Vinnie - Secaucus, NJ)
Written by: Bobby Darin; Produced by: Nik Venet
Arranged & Orchestra Conducted by: Jack Nitzsche
Recorded: April 6, 1963; Released: May 6, 1963
Eighteen yellow roses came today
Eighteen yellow roses in a pretty bouquet
When the boy came to the door
I didn't know what to say
But eighteen yellow roses came today
I opened up the card to see what it said
I couldn't believe my eyes
When I had read
Though you belong to another I love you anyway
Yes eighteen yellow roses came today
I never doubted your love for a minute
I always thought that you would be true
But now this box and the flowers in it
I guess there's nothin' left for me to do
But ask to meet the boy that's done this thing
And find out if he's got plans to buy you a ring
'Cause eighteen yellow roses will wilt and die one day...
But a father's love will never fade away
Will never fade away
"Bobby Darin-18 Yellow Roses", sound recording administered by:
EMI (thanks for allowing this to remain)
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Definitive Pop: Bobby Darin
UMG (on behalf of Rhino Elektra); BMG Rights Management, Audiam (Publishing), BMI - Broadcast Music Inc., Sony ATV Publishing, EMI Music Publishing, and 8 Music Rights Societies
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About TPC Wire & Cable Corp.
TPC Wire & Cable Corp. is a leading supplier of wire, cable and connectors used in harsh industrial environments. TPC's products are designed and engineered to withstand harsh conditions including abrasion, chemicals, constant flexing and extreme temperatures. TPC serves a variety of markets including the steel, utility, mining, automotive, food & beverage, government, oil & gas, transportation, and wood, pulp & paper markets. With an ISO 9001 Quality System and 5S (Five S) workplace organizational methods, TPC has a 120,000 square foot facility that includes a distribution center, cable assembly center and engineering testing lab.
Straight North strongly believed that demand for this niche product line was real, and created a strategy designed to avoid head-to-head competition with commodity suppliers. Extensive keyword research informed the on-site content strategy, and our off-site activities increased rankings and drove qualified traffic to the website.
Key Tactics
Earned links from prominent, authoritative manufacturing and facility safety websites.
Worked closely with client to add case study pages on its site to add credibility and increase conversions.
SALES LEADS UP
TPC's SEO lead volume has increased 129.89 percent since our campaign launch.
COST PER LEAD DOWN
Our SEO campaign produced a decrease in cost per lead of more than 50 percent – in six months.
DAY ONE ROI
Unusual for an SEO campaign, we were able to deliver a positive ROI from the first month.
After delivering a stellar website in record time, the SEO program has exceed our expectations, delivering dozens of new accounts in the first few months.
Reed Cushing, Vice President, Product and Marketing
TPC Wire & Cable Corp.


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Katherine Charlet is the inaugural director of Carnegie Endowment for International Peace's Technology and International Affairs Program. She works primarily on the security and international implications of evolving technologies, with a focus on cybersecurity and cyber conflict, biotechnology, and artificial intelligence. She most recently served as the acting deputy assistant secretary of defense for cyber policy, where she managed the development of the Department of Defense's cyber policy and strategy, the development of cyber capabilities, and the expansion of international cyber relationships.


Dr Navdeep Kaur is a general dentist who has furthered her dental education with pedodontics or children's dentistry. She has a very gentle manner and leaves kids wanting to come back to the dentist. She also does minor children's orthodontics for simple cases using dental plates and retainers.


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Biograf Caféen er en biograf i Vordingborg på Sydsjælland. Den er grundlagt i 1942 under navnet Kino.

Den har gennemgået flere ombygninger. I 1987 overtog ejerne af Bio Stege biografen og gav den sit nuværende navn.

Den har været i privateje siden 2000, hvor den har været drevet af Lone Delauran.

Referencer

Eksterne henvisninger

Biografer i Danmark
Bygninger, konstruktioner og anlæg i Vordingborg

redpajama_set_name: RedPajamaWikipedia