text:
Tript Bajwa demands for J.E.E. admission test in Punjabi too
Chandigarh, December 1: The Punjab Higher Education and Languages Minister Tript Rajinder Singh Bajwa today demanded from the Union Government's Ministry of Human Resource Development that the nation's prestigious admission test JEE (Main) should be conducted in Punjabi as in other regional languages.Mr. Bajwa has written a letter to Union Minister for Human Resource Development Sri Ramesh Pokhriyal Nishank today, saying that the admission test was initially conducted in English, Hindi and Gujarati languages. However, on the demand of the governments of different states, the Union Ministry has decided that from 2021 this entrance test would be conducted in Assamese, Bengali, Tamil, Kannada, Urdu, Marathi, Oriya and Telugu. He said that it's very unfortunate that Punjabi is not included in this list which is a matter of clear discrimination towards Punjabi Language. Higher Education Minister said that the J.E.E (main) entrance test is the nation's important test by which admissions are done in the country's leading engineering colleges and admissions in IIT institutes engineering and architectural courses.Earlier, this test was conducted by the Central Board of Secondary Education (CBSE), but now the Ministry of Human Resource Development conducts this test through the National Testing Agency (NTA).
Mr. Bajwa said that if Punjabi language is not included in the list of languages of this test, hundreds of students of Punjab would not be able to take admissions in prestigious engineering colleges of the country. If this facility is not provided to students of the state, they would have to study forcibly in English or Hindi medium which would prove a major obstacle in the development of Punjabi language.He has strongly stressed in his letter addressed to the Union Minister to take immediate stern action to add Punjabi in the list of languages of the (Main) Entrance Test so that Punjabi could also find its suitable place.

redpajama_set_name: RedPajamaCommonCrawl


text:
{{ "2019-07-08T09:00:00+00:00" | date "shortDate" }}
The Little Village of Happiness - Holly Martin
Willow McKay needs a fresh start. Her recent break-up may not have left her heartbroken, but it's certainly wounded her pride. Desperate for a change, an advert offering free homes in a picturesque village on the Cornish coast sounds like just what she needs. Without thinking twice Willow packs up her life and heads to the village of Happiness.
But when Willow arrives, she finds ramshackle cottages, shops lying empty and villagers that seem in need of cheer themselves. It's nothing like the pretty picture the advert had boasted. It seems Happiness was too good to be true. That is until she meets the handsome estate manager Andrew Harrington.
His passion for restoring the village to its former glory is contagious and soon they are working together, forming a secret society to bring happiness back to Happiness. And as sparks fly between them Willow can feel herself falling. But Andrew is holding something back.
Will they succeed in transforming the old village to its original beauty before it's too late? Can the gift of happiness really save a village, and can it save Willow herself?
"Holly Martin is a romantic genius" - Goodreads reviewer
"I absolutely loved this - it put a smile on my face from start to finish!" - Goodreads reviewer
"Just blooming delightful!!" - Goodreads reviewer
This is such a heartwarming and feel-good book. It is filled with happiness, but there are some hold back the tears moments too.
Willow McKay needs a fresh start and jumps at the chance of 12 months rent-free living in a little village on the Cornish coast. The Village of Happiness is just what she needs to mend her broken heart and revive her life. However, all is not what it seems, and she is brought back to earth with a bump on arriving at her new start life. Happiness needs to be injected into the Village of Happiness and Willow is determined to make this happen. Along with her new partner in crime, Andrew, she sets to making a plan and if she has some fun herself along the way, would that be so bad or is it too soon?
Willow's character is full of joy, and she is so optimistic. This can go wrong in writing, and that character can end up being a bit too saccharine; however, Holly Martin gets the balance just right with Willow. She is really loveable, relatable and a genuinely nice person. Andrew also is really well-written. He has his own demons to come to terms with and it was really nice to read about this obstacle that so many people face. It was lovely to read the author's note at the end about all the research she did into Andrew's condition. It's always great to know the author has put effort into making sure the book is as accurate for the reader as possible.
I loved the camaraderie between Andrew and Willow; the honesty between them was a breath of fresh air. They said what they wanted and threw caution to the wind. In so many romance books, there is so much misunderstanding because the characters don't say what they are feeling or thinking, and it can be frustrating. There is none of that frustration here, just two people speaking up for what they want.
Overall, this was a fantastic, enjoyable book that put a smile on my face. I am very much looking forward to book two in the series and seeing what the author has in store for Willow's friend Ruby and Andrew's brother Jacob. Will they change their ways and settle down or is their attraction headed for disaster?
Holly lives in a little white cottage by the sea. She studied media at university which led to a very glitzy career as a hotel receptionist followed by a even more glamorous two years working in a bank. The moment that one of her colleagues received the much coveted carriage clock for fifteen years' service was the moment when she knew she had to escape. She quit her job and returned to university to train to be a teacher. Three years later, she emerged wide eyed and terrified that she now had responsibility for the development of thirty young minds. She taught for four years and then escaped the classroom to teach history workshops, dressing up as a Viking one day and an Egyptian High Priestess the next. But the long journeys around the UK and many hours sat on the M25 gave her a lot of time to plan out her stories and she now writes full time, doing what she loves.
Holly has been writing for 8 years. She was shortlisted for the New Talent Award at the Festival of Romance. Her short story won the Sunlounger competition and was published in the Sunlounger anthology. She won the Carina Valentine's competition at the Festival of Romance 2013 with her novel The Guestbook. She was shortlisted for Best Romantic Read, Best eBook and Innovation in Romantic Fiction at the Festival of Romance 2014. She is the bestselling author of 22 books
Written by Helen


text:
Q: Problem aligning text and table vertically I'm trying to make a page heading using
\documentclass[12pt]{article}

\usepackage{sidecap,wasysym,array,caption,graphicx}
\usepackage[a4paper,margin=1cm,footskip=.5cm]{geometry}
\pagenumbering{gobble}

\newcommand\textbox[1]{%
  \parbox[t]{.333\textwidth}{#1}%
}

\begin{document}

\noindent\textbox{Date: \begin{tabular}[t]{|l|l|l|l|l|l|}
                        \hline
                        & & & & & \\
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                        \hfill\textbox{\hfil \textsc{\LARGE Content}\hfil}\textbox{\hfill\LARGE\smiley{}}

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in which I'm trying to make a box using a table, to fill in the date. But the box and the text "Date:" don't seem to align. I already tried doing Align text and image on the same line? but I'm not sure if it is the right way to go about it. How can I align the "Date:" and the table in the same line?

A: The top element of the table is not the first row, but the line above it.
Usually a tabular row has a strut with .7\baselineskip as height and .3\baselineskip below (multiplied with \arraystretch).
Since digits usually do not have descenders, the following example aligns the table at the bottom line, but moves it down 2/3 of the descender (.2\baselineskip) as compromise:
\documentclass[12pt]{article}

\usepackage{sidecap,wasysym,array,caption,graphicx}
\usepackage[a4paper,margin=1cm,footskip=.5cm]{geometry}
\pagenumbering{gobble}

\newcommand\textbox[1]{%
  \parbox[t]{.333\textwidth}{#1}%
}

\begin{document}

\noindent
\textbox{%
  Date: %
  \raisebox{-.2\baselineskip}{%
    \begin{tabular}[b]{|l|l|l|l|l|l|}
      \hline
      & & & & & \\
      \hline
    \end{tabular}%
  }%
}%
\hfill
\textbox{\hfil \textsc{\LARGE Content}\hfil}%
\textbox{\hfill\LARGE\smiley{}}

\end{document}

redpajama_set_name: RedPajamaStackExchange


text:
A gang bang is a situation where one person has sexual intercourse with more than two partners.

Gang bang may also refer to:

Crime
Gang banging, the act of engaging in violence and other criminal activies as a member of a street gang.

Music
Gang Bang, 1999 album by René Berg

Songs
 "Gang Bang" (song), a 2012 song by Madonna
"Gang Bang", a 1972 song by Oscar Brown Jr. from Movin' On
"Gang Bang", a 1974 song by The Sensational Alex Harvey Band from Next
"Gang Bang", a 1994 song by Brand Nubian on Everything is Everything
"Gang Bang", a 1996 song by Dr. Dre and World Class Wreckin' Cru
"Gang Bang", a 2005 song by French band Indochine on Alice & June
"(Having a) Gangbang", a song by Black Lace featured in the 1987 film Rita, Sue and Bob Too
"Gang Bang", a 2012 song by Wiz Khalifa
"Gang Bang", a 2013 song by Bob Seger

See also
Bang Gang, an Icelandic band
Gang banger (disambiguation)

redpajama_set_name: RedPajamaWikipedia


The United States is a young country with an old history. Rising to the highest heights of power in the blink of an eye through rapid expansion across a broad land rich in natural resources, achieving unity more than 100 year before the much more ancient Europe even made a start at it, and now prematurely gray as it struggles to adapt to a global economy and a shattered self-image, the American story has been a tough one to tell. The mirrors held up to Americans have often been fractured and one-dimensional, and perhaps with the exception of the Great American Novel, Huckleberry Finn, no work of art has broken through as a wide-ranging reflection not only of who we want to be, but also of who we really are. So it may be a bold declaration to make, but if I had to pick the one work that has been and will continue to be the greatest telling of the Great American Story, it would be West Side Story.
Many great musicals have plots packed with drama and unlikely coincidences. By contrast, on the surface anyway, 'Meet Me In St Louis' has almost no plot at all. However, there is far more to this holiday classic, starring Judy Garland in one of her best-loved roles, than meets the eye on first viewing. Producer Arthur Freed, director Vincente Minnelli and the team at MGM agonised over the ingredients just as the Smith household's cook, Katie (Marjorie Main) worries over her homemade ketchup bubbling on the stove in the film's opening scene.
Katie is afraid the ketchup may be too sweet. MGM's powers-that-be saw the same danger in this adaptation of writer Sally Benson's humorous 'Kensington' magazine stories, recalling her girlhood in St Louis at the turn of the 20th century. Various scriptwriters were drafted in and encouraged to add exciting plot twists, such as an unlikely blackmail plot involving a Colonel, to make the mixture a little stronger.
I sat down with my 3-year old daughter the other day and invited her to watch a dancing scene from Swing Time with me. She's very interested in dance these days and taking a class (ballet) so I figured I would show her. It was the scene where Fred and Ginger are doing the "Pick Yourself Up" number, which is a boisterous dance. My daughter asked me a few questions about the movie at first as Fred and Ginger were talking, but she was mostly entranced and watched the scene with me in silence during the dance itself. I know it sounds simple, but I realized for the first time that dancing requires little explanation or greater understanding of context and/or plot to really understand it. It is truly a physical communication to those of us in the audience. Even small children instinctively know how to dance. It's not something you have to teach them. Dancing speaks to us on an instinctive level, and there never was, nor will there ever be another dancing duo like Fred Astaire and Ginger Rogers, whose chemistry and artistry remain unsurpassed.
Note: The following is an interview conducted over the summer at the Happy Dale Nursing Home in Des Moines, Iowa with 86 year-old Agnes Ferber, niece of celebrated writer Edna Ferber. Ms. Ferber is professor emeritus at Drake University, specializing in theatre and cinema studies. Ms. Ferber, who retired in 1987, has spoken about her aunt's work at a number of universities across the country, and has more than an affectionate regard for James Whale's 1936 film version of 'Show Boat,' which is based on her most celebrated work. The loquacious and fecund scholar magnanimously agreed to share her opinions on the film's music, historical context and artistry for the musical countdown.
SJ: Hello Ms. Ferber. I want to thank you for agreeing to impart your vast wealth of information, experience and insight into your aunt's most famous work and the famed stage and film versions that widened it's cognizance worldwide.
AF: Young man -or I can call you that compared to where I have progressed to- the honor is mine. I understand you are doing some kind of a musical countdown, and the 1936 version of Show Boat is expected to do quite well.


I've been searching other hacks also and all of them dont work, crash gmod, or delete hl2.exe I hope this isnt one of them but i have high hopes. Anyways what other hacks have you been disapointed in?
This hack rarely crashes or doesn't work.
I don't know. But you'll find good ones! I hav e sir. I don't know. But you'll find good ones! I have sir. I don't know. But you'll find good ones! I have sir.


text:
This Is the Favorite College Major of Psychopaths, According to Science
Not all majors are of equal interest to those with dark personalities.
Researchers have long known that psychopaths aren't evenly distributed throughout the population. Yes, you're likely to meet lots of card-carrying psychos in prison, but some legitimate professions have way more than their fair share.
And sorry, business leaders, but executive actually tops the list of jobs with the highest proportion of psychopaths. While the incidence of psychopathy among the general population is only one percent, some studies show triple or quadruple that percentage of business leaders are psychopaths. Even more alarming research claims that one in five corporate leaders qualifies as having a high level of psychopathic traits.
Why is that? Is it there something about the business world that transforms nice, well-meaning young people into ruthless psychos? Or is it instead that ruthless psychos are attracted to careers in business as the perfect venue for their inclinations? A group of Danish researchers recently determined to find out.
What came first, business leadership or psychopathy?
The researchers rounded up more than 400 students who were about to start one of five declared majors -- psychology, politic science, business, economics, or law. They then tested the students for the so-called dark triad of personality traits to get a sense of their levels of narcissism, Machiavellianism, and psychopathy.
The results won't do much to soothe those concerned about the personalities of those that sit atop many of the world's businesses. Those enrolled in business and economics showed, by far, the highest levels of dark personality traits. Law was in the middle. Would-be psychologists were the least psychopathic of the lot.
That suggests it's not something about the culture of business that's turning people into psychopaths (though business training could conceivably reinforce these tendencies). Instead, it seems that those with this sort of drive to power naturally gravitate to the majors that seem most suited to the expression of these characteristics.
"The desire for power, status, and money characterizing dark triad individuals may steer them toward, for example, economics, business, and law educations because these educations pave the way for a career in the corporate world, and the corporate world generally rewards self-serving behavior and provides an environment in which individuals with dark personalities can make use of their qualities and succeed," commented the researchers.
Though that shouldn't be taken to mean that budding psychopaths are sitting around drumming their fingers Dr. Evil-style and consciously planning domination through business leadership.
"I don't think it's a conscious or deliberate choice to be manipulative or express a 'bad' part of their personality that seeks power," explained Anna Vedel, the study's co-author. "I think it's probably more of a subconscious thing, allowing them to pursue careers in an environment that matches their worldview."
So, are you currently working with a junior psychopath in training? Here's a handy checklist to help you determine if your boss or co-worker is a garden-variety jerk or actually qualifies as a full-blown psycho.


Give your children what they really want: your time, energy and focus.
As I've worked with families all over this country organizing their homes, almost everywhere I have gone I have seen moms and dads struggling and muddling through mountains of toys that they have worked to supply to their kids. And from my perspective those parents rarely receive their kids' appreciation for all the stuff they've been given.
Parents feel that if they don't get their kids all these toys, educational games, and computer programs, they are depriving their kids of the opportunities that they, the parents, missed.
I suggest a paradigm shift: focus on giving your kids what you have, instead of focusing on providing them with what you did not have. Why give your kids something that is perishable that will just add to the junk heap in some landfill, when you can give them the lasting treasures of your time, energy, and focus.
Take them to the zoo. Walk or hike with them in a park or on a trail. Get them off the computer and into the car for a trip to a bookstore or for ice cream. Teach them how to serve by guiding them into helping others a couple of hours each month. Commit to having just plain good family time once a week at home without turning on the TV. Establish family traditions that they will remember for years to come.
There are so many things you can do that does not involve stuff. When I was growing up, more than anything that my dad ever bought for me, I wanted him to play ball with me and the neighborhood kids. I wanted time with him.
Cultivate an ever-deepening friendship with your children. It's not time spent; it's time invested. And all the while you will model for your children how the really important things in life have little to do with stuff that will be enjoyed momentarily before it's soon set aside or discarded.
If you invest your time wisely, they will, too. They will grow up and tell their children stories, not about the stuff they didn't have, but all the wonderful joys and memories of what you gave them. These are treasures that you can never buy in a store. Your children will love you all the more for it, I guarantee!


Event held on April 26, from 9.15 to 11.00, at Rue de la Science 23, 5th floor, 1040 Brussels.
Buildings are not just stand-alone units using energy from the grid. They are entering a transition phase by becoming micro energy-hubs consuming, producing, storing and supplying energy more flexibly than before. Whether or when this transformation will really happen depends to a large degree on the implementation of supportive policies.
Through this event we aimed to foster a critical discussion around the definition of the smart buildings' concept and the vision for the future built environment. These lingering questions together with the concretisation of the "smartness indicator" set out in the 'Clean Energy for All Europeans' package were the main topics tackled. Further tangible recommendations of what can be done at the EU level to bolster smart buildings and their associated benefits was also discussed.
Please find the agenda and presentations below.
What is needed at the European level to support and boost the transition to smart buildings?


Test it as many times as you need and set this page as your homepage. There are multiple clients available for free online. These are the sites you will find when doing a web search for torrent trackers. It is available in multiple domains and with ssl protection to safeguard your searches. Some trackers have a rating system which allows users to vote on if the file is good or not.
It is one the best Torrentz alternatives we have tried so far and offers an illustrious torrent library. You can find the and get awesome search engines for torrenting. Update: List of top is now out. Traffic encryption can solve this, but it may or may not work in your specific circumstances. Thanks to this engine my service is able to help all people who look for live torrents. Finally, also deserves a mention. A few weeks ago all links to externally hosted torrents were removed, as was the list of indexed pages.
Copy the list of trackers to your clipboard. RuTracker RuTracker is a Russian torrent website and has been a fan favorite among file sharing community. Torrents can be used to transfer any file type. This is the second incident that we have witnessed where a famous torrent website has been taken down. Thanks to this search engine you will receive a list of live torrents, click the one search result to visit the popular torrent site and download magnet link. This file does not contain the content that you are downloading. I regularly update a list of supported torrent sites, so I would say you get results more often, even in hard phrases.
The site has been around for quite a few years already but never made it into the top ten before. Instead of visiting many torrent sites and seeing a variety of ads, you will visit only one website with updated and working torrent. It offers numerous torrents and can be used a search engine and also as a torrent directory. More intensive applications such as streaming video and playing games may benefit from exiting the torrent application first. The list is based on various traffic reports and we display the Alexa rank for each. The past year has been relatively quiet for the notorious torrent site, which is currently operating from its original.
Rather than a conventional BitTorrent indexing site, Torrentz. LimeTorrents LimeTorrents offer hundreds and thousands of torrents to download and upload. This section needs additional citations for. Once the download is complete, you can use the files that you downloaded as you normally would. Add more trackers to the torrent.
This is especially important for video files. Update: ExtraTorrent has steadily grown its userbase over the past several years and this trend continues. You can use these clone websites as an alternative to Torrentz. One of the distinct features of Demoniod is its feature to upload torrent files. As I said, the engine is powered by Google Custom Search, but why this service is much better to find torrents than the normal Google search? Find a torrent tracker website. Zooqle If you are looking for a slick and easy to use torrent website, then give Zooqle a try. Leave your torrent client running in the background.
Is Torrentz4 legit and safe? Torrentz 4 reviews and fraud and scam reports. Torrentz4.eu review.
From here you can limit the download speed and upload speed. Because of their public nature, many torrents are tracked by copyright holders, and downloading them can result in action from your internet service provider. Now, before panic sets in, we took the liberty of compiling the 20 best Torrentz alternatives for you. If there are significantly more leechers than seeders, the amount of bandwidth you receive will be lower, resulting in slower downloads. If the torrent has regular subtitles they come as an. It provides the exact same experience as Torrentz but does not allow bookmarks, comments, or votes to users as yet.
It indexed from various major torrent websites, and offered compilations of various trackers per torrent that were not necessarily present in the default file, so that when a tracker was down, other trackers could do the work. They are old and indexed so Google shows them, new and fresh torrents might be invisible for you even if they are also indexed. This meta-search engine copied the look and feel of the defunct meta-search engine and covers dozens of extra sites compared to its predecessor. Type of site Torrent meta-search engine Available in English August 5, 2016 2016-08-05 Created by Flippy alias Website. Torrent clients will automatically try to download at the fastest speed allowed by your connection. There's no central server involved; data is downloaded from other users seeders.
If yours is not, you can drag the torrent file into the client window to add it to the download queue. Mininova strives to keep the website clean and family-safe, and does not permit any submission involving adult content. Most Popular Torrent Sites 1. In this Article: There are many ways to download movies, music, books, and software for free. Make sure that you can run the content. It also offers magnet links of torrents and you can use them to directly add the.


text:
Die Gemeinde Fushë Kosova (, ) ist eine Gemeinde im Kosovo. Sie liegt im Bezirk Pristina. Verwaltungssitz ist die Stadt Fushë Kosova.

Die Gemeinde ist 1988 gegründet worden, davor gehörte das Gebiet zur Gemeinde Pristina.

Geographie
Die Gemeinde Fushë Kosova befindet sich im Zentrum des Kosovo. Im Süden grenzt sie an die Gemeinde Lipjan, im Osten an die Gemeinden Pristina und Gračanica, im Norden an die Gemeinde Obiliq und im Westen an die Gemeinde Drenas. Insgesamt befinden sich 15 Dörfer in der Gemeinde, ihre Fläche beträgt 83 km². Zusammen mit den Gemeinden Pristina, Podujeva, Drenas, Obiliq, Lipjan, Gračanica bildet die Gemeinde den Bezirk Pristina.

Bevölkerung
Die aktuellste amtliche Schätzung von 2020 beziffert die Einwohnerzahl der Gemeinde auf 39.948.

Die letzte Volkszählung aus dem Jahr 2011 ergab für die Gemeinde Fushë Kosova eine Einwohnerzahl von 34.827, davon bezeichneten sich 30.275 als Albaner (86,9 %), 3230 als Aschkali (9,3 %), 436 als Roma (1,3 %), 321 als Serben (0,9 %), 282 als Balkan-Ägypter (0,8 %) und 111 als Angehörige anderer Nationalitäten.

34.019 deklarierten sich als Muslime, 428 als Orthodoxe, 71 als Katholiken, 218 gaben keine Antwort oder waren konfessionslos.

Orte
Die Liste der Orte in der Gemeinde Fushë Kosova enthält die 16 Orte, in die sich die Gemeinde gliedert.

Weblinks

 Berichte des Instituti GAP zur Gemeinde Fushë Kosova (albanisch)
 Bericht der OSZE von 2018 zur Gemeinde Fushë Kosova (englisch)

Einzelnachweise

Fushë Kosova


text:
Sailing with the Schooner Zodiac and their Spring Lighthouse Tour
I have a strong fascination for lighthouses and the people that cared for them, with their unique and romantic, sometimes tragic, lifestyle and history. In fact, not only did my husband and I get married at a lighthouse, but we recently completed my Bucket List item of touring all the lighthouses in the State of Washington that you can visit. However, it wasn't until just recently, that I had the opportunity to see some of these scenic lighthouses from the point of view of the sea, and from the perspective of the sailors who had relied upon, and continue to do so, these important structures for navigation and landmarks. From aboard the impressive 160-foot sailing vessel with four majestic sails, the Schooner Zodiac, on their four-day Spring Lighthouse Tour, I gained an even bigger appreciation for the powerful lights beaming from the legendary lighthouses, and for the sounds of the mighty fog horn. Even with the modern technology of radar, GPS, radio communication, and even apps on cell phones, lighthouses are still essential at night, in the fog, or in inclement weather.
It wasn't just the lighthouses though that made my excursion on the Schooner Zodiac memorable around the San Juan Islands in Washington State. It was the historic Schooner Zodiac itself. It was her people, her educational aspect, her history, and her grandeur that were evident from the time I boarded, to the couple of times we hoisted the 127-foot tall, 7,000 square feet of sails, to the restful nights being lulled to sleep by the gentle rocking of the ship. (Although one of the nights it was a bit rockier due to some windier conditions.)
In our four days on the seas, the Schooner Zodiac took me, my husband, other passengers, guests, and the crew to see eight lighthouses and light stations, three of which we were also able to visit on land via their Zodiac Tender, a small motorboat, where we donned lifejackets to make it to shore. We sailed from picturesque island to picturesque island by day, and anchored at peaceful secluded coves by night, including Hughes Bay at Lopez Island, Port Townsend, and Prevost Harbor at Stuart Island. When the weather was clear and warm, and the skies and water were both a rich blue, we had glimpses of Mount Baker and the Olympics Mountains. Even when we were greeted by the fog in the mornings, and the wind was stronger and the air was colder, all the realities of sailing made my four days on the Schooner Zodiac an exciting adventure. We also had a few chances to kayak, we stretched our legs for an hour at Roche Harbor, we saw a pod of porpoises, a convocation of eagles and seagulls feeding on fish, and enjoyed the ability to see abundant stars at night. (We unfortunately did not see any whales this trip, but that is a certainly a possibility in these waters.)
It was also the people, all of us in fact, crew and passengers alike, that added to the ambiance of the journey. From the helpful and hospitable captain, to the talented cook, to the knowledgeable volunteer crew. There were even a couple of people aboard the ship who work closely with lighthouses as volunteers and were able to provide us with deeper information about the lighthouses. The passengers were fun group, too. With the age ranges of both the crew and passengers from their 20's to their 80's, we got samples from fun and laughter, to hearing sailing stories of the wise and experienced.
We passengers had the opportunity to learn about sailing and to participate in what it takes to make the Schooner Zodiac sail. In four half-hour shifts, each passenger had a "watch rotation." One rotation was a lesson in navigation through charts, radar, compass, and other means. We each got a turn at steering the helm, sometimes using a landmark when the weather was clear to steer by, other times by using a compass in the fog. Doing a bow watch from the front of the ship looking for debris, kayaks, other boats, whales, or anything that might be in the way, was our third rotation. And being a quarterdeck messenger between the bow and the person steering and navigating at the helm was the fourth.
Each passenger also had a "sailing station" when it came time to "prepare to make sail." When they called "all hands on deck," we made our way to participate in something that, from someone who had never done this before in her life, I thought was amazing, and gave me a rush of excitement. My sailing station was the "staysail," where with one crew member, he instructed me on when to pull the line to raise the sail, and how to belay and do a locking hitch of the line to complete the process. All passengers participated in raising the "mainsail," by teaming up together on one of two sides, pulling a thick line, heaving the heavy sail as it rose in the wind. This took my breath away, both literally from the hard work it was to pull that heavy line, and figuratively from seeing the white sails breathing as they rose in the wind against the blue sky.
And when they called "all hands stand down," I asked my instructional crew member, well, I have always either stood up or sat down, but I had never stood down before. So what did that mean? It meant that I could go back to doing whatever I was doing before the call was made for "all hands on deck." So I usually returned to taking lots of photographs.
One morning all passengers were able to contribute to the preparations of cleaning the deck, polishing the brass, and getting the Schooner Zodiac ready for the day. I must say that in four days' time, I learned more about sailing and navigation and boats and weather than I personally ever have in my life. Even all of the words and terminology I just described, I have never written before. Very educational.
The Schooner Zodiac itself was originally launched in 1924 in Maine as a private luxury yacht for the heirs of Johnson & Johnson. The Zodiac's history also includes coming in fourth place in the 1928 Transatlantic Race for the Kings Cup, and sailing off the Golden Gate in San Francisco for 40 years as a pilot schooner. She was retired in 1972, but has been lovingly restored to its majesty of the 1920's, with its intricate mahogany, oak, and teak wood detail both inside and out, along with modern conveniences, including showers, and delicious food prepared by the previously-mentioned talented cook. Sailing out of Bellingham, Washington, the Schooner Zodiac was placed on the National Register of Historic Places in 1982.
My fascination for lighthouses continues. And thanks to my sailing with the Schooner Zodiac's Spring Lighthouse Tour, it has now grown with appreciation to include not only seeing the lighthouses from the sailor's point of view, but also from gaining some skills and knowledge of what it takes to be a sailor on a ship out on the waters that also seem to have its own unique and romantic, sometimes tragic, lifestyle and history.
I was provided this excursion courtesy of Bellingham Whatcom County Tourism and the Schooner Zodiac, but all opinions are my own. For more information about sailing with the Schooner Zodiac, please visit their website, www.schoonerzodiac.com, which includes a list of all upcoming cruises from now through October, from their day sails, to their three day trips, to trips of longer durations, from the San Juan Islands to the Canadian Gulf Islands. The ship carries up to 26 passengers on overnight cruises in berths or private rooms, and up to 49 passengers on day sails.
List of lighthouses in the order of my pictures above, with the number of pictures of each lighthouse:
Burrows Island Lighthouse (2)
New Dungeness Lighthouse (3)
Point Wilson Lighthouse (2)
Lime Kiln Lighthouse (3)
Smith and Minor Islands (2)
Turn Point Lighthouse (2)
East Point Saturna Island Canada (2)
Patos Island Lighthouse (3)
Learning Some Sailing Skills Aboard The Schooner Zodiac
Point Wilson Lighthouse and Marrowstone Point Lighthouse near Port Townsend
This entry was posted in San Juan Islands, Seattle, Puget Sound & Washington State and tagged Lighthouses, Puget Sound, San Juan Islands, Seattle, Washington State by debbysdepartures. Bookmark the permalink.
6 Replies to "Sailing with the Schooner Zodiac and their Spring Lighthouse Tour"
Nancy on April 21, 2016 at 12:46 pm said:
Beautiful. That's just way too cool! Travel on Debby!
debbysdepartures on April 21, 2016 at 6:10 pm said:
Thanks. I know. Thanks!
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text:
Włodzimierz Stanisław Szomański (ur. 8 listopada 1948 w Warszawie, zm. 1 maja 2014 tamże) – polski muzyk, wokalista, kompozytor, pedagog i aranżer, założyciel i lider grupy muzycznej Spirituals Singers Band, ojciec Olgi Szomańskiej.

Życiorys
Ukończył studia w Państwowej Wyższej Szkole Muzycznej we Wrocławiu w 1971, następnie pracował jako nauczyciel wychowania muzycznego w X Liceum Ogólnokształcącym we Wrocławiu i jako instruktor muzyczny wrocławskich zespołów estradowych. W latach 1974-82 śpiewał w kierowanym przez Edmunda Kajdasza chórze Cantores Minores Wratislaviensis. Od 1978 kierował założonym przez siebie zespołem Spirituals Singers Band, który początkowo działał jako grupa wokalno-instrumentalna później już tylko wokalna wykonująca utwory a cappella lub z towarzyszeniem orkiestry. Zespół pod kierownictwem Szomańskiego posiadał szeroki repertuar utworów począwszy od takich gatunków jak negro spirituals czy gospel poprzez standardy jazzowe, evergreeny muzyki rozrywkowej oraz kolędy i pieśni religijne. Skomponował wiele z utworów i aranżacji wykonywanych przez ten zespół. Wraz z zespołem występował na festiwalach w kraju i za granicą min. Jazz Jamboree, Wratislavia Cantans, Złota Tarka oraz na festiwalu w Sopocie.

Był także autorem muzyki do wystawianych na deskach wrocławskich teatrów przedstawień min. Ptak Cis (1987) i Pociąg do Betlejem, czyli 715 zaginął  (1993) Joanny Kulmowej, Pan Cogito wędrowiec (1990) Zbigniewa Herberta, Noc Walpurgii albo kroki komandora (1990) Wieniedikta Jerofiejewa, Poskromienie złośnicy (1995) Williama Szekspira, Okno na parlament (1995) Raya Cooney'a.

Do jego najważniejszych kompozycji zalicza się napisaną w 2000 z okazji obchodów tysiąclecia Wrocławia Honorificabilitudinitatibus oraz Missa gospel's (2001), oratoria Jutrznia gospel's (2004), Madonny Jana Pawła II (2006) i Litania do Św. Polskich – Santo Subito.

W 2013 w został odznaczony Brązowym Medalem "Zasłużony Kulturze Gloria Artis", nadanym przez Ministra Kultury i Dziedzictwa Narodowego "za wybitne zasługi dla promocji kultury polskiej, szczególnie chrześcijańskiej, w kraju i poza granicami".

Zmarł w wyniku obrażeń doznanych w czasie wypadku samochodowego, gdy jechał wraz z zespołem do Siedlec na zaplanowany koncert.

Został pochowany 10 maja 2014 na cmentarzu św. Wawrzyńca we Wrocławiu.

Przypisy

Absolwenci Akademii Muzycznej im. Karola Lipińskiego we Wrocławiu
Muzycy związani z Wrocławiem
Nauczyciele związani z Wrocławiem
Odznaczeni Brązowym Medalem "Zasłużony Kulturze Gloria Artis"
Pochowani na cmentarzu św. Wawrzyńca we Wrocławiu
Polscy aranżerzy
Polscy kompozytorzy jazzowi
Polscy wokaliści jazzowi
Polskie ofiary wypadków drogowych
Urodzeni w 1948
Zmarli w 2014
Ludzie urodzeni w Warszawie


As winter nears, I have packed up my "hot wax"/encaustic painting set up until spring and have been experimenting with "cold wax"/oil paints and am having a wonderful journey. My work is headed in a direction I've always wanted to be - simple. The pieces are coming out with a more minimalist style. Mission accomplished. It's not that I disliked my mixed media paintings that were more on the busy/involved side, I just felt it was time for a change - actually that change was inside of me and happens to be coming out through my art. Here are some pics that don't do the subtle layers justice but as you can see, the landscape series I'm working on still has a lot of texture within, except it's more subtle. Peaceful.


text:
4-Bromo-4'-methoxy-1,1'-biphenyl
Bromides Ethers Benzene Compounds
Formula : C13H11BrO Boiling Point : -
Linear Structure Formula : - InChI Key : -
Precautionary Statements: P233-P260-P261-P264-P271-P280-P302+P352-P304-P304+P340-P305+P351+P338-P312-P321-P332+P313-P337+P313-P340-P362-P403-P403+P233-P405-P501 UN#:
Hazard Statements: H315-H319-H335 Packing Group:
Upstream synthesis route of [ 58743-83-2 ]
[ 58743-83-2 ] Synthesis Path-Upstream 1~2
Reference: [1] Chemistry - A European Journal, 2009, vol. 15, # 17, p. 4289 - 4300
[2] RSC Advances, 2016, vol. 6, # 97, p. 95137 - 95148
Reference: [1] Molecular Crystals and Liquid Crystals (1969-1991), 1985, vol. 131, p. 1 - 8
[ 58743-83-2 ] Synthesis Path-Downstream 1~26
[2]Journal of Heterocyclic Chemistry,2001,vol. 38,p. 11 - 23
[3]Journal of the Chemical Society,1936,p. 802,806
[4]Molecular Crystals and Liquid Crystals (1969-1991),1985,vol. 131,p. 1 - 8
81% Stage #1: 4-bromo-4'-methoxylbiphenyl With n-butyllithium In tetrahydrofuran; hexane at -76℃; for 0.666667h; Stage #2: Diethyl carbonate In tetrahydrofuran; hexane at 25℃; for 1h; Inert atmosphere; Synthesis of 26 n-BuLi (2.7M solution in hexane, 1.5 mL, 1.1 equiv) was added over 10 min to a solution of 25 (0.90 g, 3.4 mmol) in dry THF (15 mL) at -76 °C. The reaction was allowed for 40 min. A solution of diehtylcarbonate (0.13 mL, 1.1 mmol) in dry THF (2 mL) was dropwised to the reaction mixture. And then the reaction mixture was stirred at room temperature for 1 h under Ar. The solution was poured into brine (10 mL) and CHCl3 (20 mL). Aqueous layer was extracted with CHCl3 for two times. The combined organic layer was washed with water and dried over MgSO4. A residual liquid was purifiedby column chromatography (EtOAc/Hex = 1/5) to give the compound 26 (0.51 g, 81%).
With sodium; benzene
Reference: [1]Kim, Nam-Kyun; Sogawa, Hiromitsu; Takata, Toshikazu [Tetrahedron Letters, 2020, vol. 61, # 23]
[2]Morton; Emerson [Journal of the American Chemical Society, 1938, vol. 60, p. 284]
With potassium carbonate; In N-methyl-acetamide; water; Part A: To a solution of 12.4 grams (5.0 mmol) of 4-(4'-bromophenyl)phenol in 50 mL of dimethylformamide was added 10.1 grams of potassium carbonate followed by 10.51 grams of iodomethane and this stirred at room temperature for 48 hours. The solution was diluted with 400 mL of water and extracted with ethyl acetate. The organics were dried over magnesium sulfate filtered and concentrated to yield 14.1 grams of crude product. Purification by recrystallization from ethyl acetate hexane gave 8.2 grams of 4-(4'-bromophenyl)anisole as a white crystalline solid.
Reference: [1]Journal of Heterocyclic Chemistry,2007,vol. 44,p. 853 - 862
[3]Chemical Communications,2015,vol. 51,p. 12641 - 12644
[4]Molecular Crystals and Liquid Crystals (1969-1991),1985,vol. 127,p. 413 - 430
[5]Journal of Fluorine Chemistry,2006,vol. 127,p. 620 - 626
[6]Patent: US6747027,2004,B1
95% Stage #1: 4-bromo-4'-methoxylbiphenyl With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at 20℃; for 4h; Further stages.;
(i) nBuLi, Et2O, benzene, (ii) /BRN= 1209232/; Multistep reaction;
Reference: [1]Moon, Kyung-Soo; Kim, Ho-Joong; Lee, Eunji; Lee, Myongsoo [Angewandte Chemie - International Edition, 2007, vol. 46, # 36, p. 6807 - 6810]
[2]Baker,R. et al. [Journal of the Chemical Society, 1964, p. 627 - 633]
60% With tetrakis(triphenylphosphine) palladium(0); silver(l) oxide In tetrahydrofuran at 60℃; for 36h;
60% With silver(l) oxide In tetrahydrofuran at 60℃; for 36h;
Reference: [1]Hirabayashi, Kazunori; Mori, Atsunori; Kawashima, Jun; Suguro, Masahiro; Nishihara, Yasushi; Hiyama, Tamejiro [Journal of Organic Chemistry, 2000, vol. 65, # 17, p. 5342 - 5349]
[2]Hirabayashi, Kazunori; Kawashima, Jun; Nishihara, Yasushi; Mori, Atsunori; Hiyama, Tamejiro [Organic Letters, 1999, vol. 1, # 2, p. 299 - 301]
67% Stage #1: 4-bromo-aniline With tert.-butylnitrite; boron trifluoride diethyl etherate In methanol at 0℃; for 0.5h; Schlenk technique; Stage #2: 4-methoxyphenylboronic acid In methanol at 0 - 60℃; for 5h; Schlenk technique;
65% Stage #1: 4-bromo-aniline With tert.-butylnitrite; boron trifluoride diethyl etherate at -15 - 5℃; for 0.583333h; Stage #2: 4-methoxyphenylboronic acid With (R,R)-N,N'-(2-MeC6H4)2-N,N'-(cyclohexane-1,2-diyl)thiourea In methanol at 20℃; for 4h;
Reference: [1]Zong, Yan; Hu, Jiefeng; Sun, Peipei; Jiang, Xiaoqing [Synlett, 2012, vol. 23, # 16, p. 2393 - 2396]
[2]Dai, Mingji; Liang, Bo; Wang, Cuihua; Chen, Jiahua; Yang, Zhen [Organic Letters, 2004, vol. 6, # 2, p. 221 - 224]
1: 30% 2: 22% With disodium[(N,N'-bis(2-hydroxy-5-sulfonatobenzyl)-1,2-diphenyl-1,2-diaminoethano)palladate(II)]; caesium carbonate In water at 80℃; for 1h; Catalysis experiments and gas chromatographic analysis of the reaction mixtures General procedure: Stock solutions of the catalysts (Na2[Pd(HSS)], Na2[Pd(PrHSS)], Na2[Pd(BuHSS)],Na2[Pd(dPhHSS)], rac-Na2[Pd(CyHSS)], Na2[Pd(cis-CyHSS)]) Na2[Pd(trans-CyHSS)]) were prepared by dissolving 5.0×10-7 mol complex in 6 mL water. In general, 0.5 mmol aryl-halide, 0.75 mmol boronic acid derivative (1.5 mmol in the reactions of aryl-dihalides), and 0.5 mmolbase (Cs2CO3) were used in each reaction. Good quality distilled water was used as solvent, the organic phase was comprised of the substrates. 3 mL of water was used in each reaction. The reactions were carried out at 80 °C in 30-120 min reaction time. At the end of the reactions, the mixtures were allowed to cool to room temperature and then were extracted by chlorofom (2 mL). After separation of the phases (15-20 min) the organic phase was removed by a Pasteur pipette and filtered through a short MgSO4 plug.
With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In methanol; toluene Heating;
Reference: [1]Bunda, Szilvia; Joó, Ferenc; Kathó, Ágnes; Udvardy, Antal; Voronova, Krisztina [Molecules, 2020, vol. 25, # 17]
[2]Sinclair, David J.; Sherburn, Michael S. [Journal of Organic Chemistry, 2005, vol. 70, # 9, p. 3730 - 3733]
Reference: [1]Journal of Heterocyclic Chemistry,2001,vol. 38,p. 11 - 23
Reference: [1]Molecular Crystals and Liquid Crystals (1969-1991),1985,vol. 131,p. 1 - 8
4-bromo-2-methyl-2H-pyrazol-3-ylamine [ No CAS ]
(4-bromo-2-methyl-2H-pyrazol-3-yl)-(4'-methoxy-biphenyl-4-yl)-amine [ No CAS ]
With sodium t-butanolate In toluene at 80℃; for 48h; 1.19 Example 1.19; Preparation of (4-Bromo-2-methyl-2H-pyrazol-3-yl)-(4'-methoxy-biphenyl-4-yI)-amine(Compound 13).A 20-mL scintillation vial was charged with 4'-bromo-4-methoxy-biphenyl (263.1 mg, 1 mmol), 3-amino-4-bromo-2-methyl pyrazole (176.0 mg, 1 mmol), sodium fert-butoxide (134.5 mg, 1.4 mmol), tris(dibenzylideneacetone)dipalladium(0) (45.8 mg, 0.05 mmol), BESfAP (62.3 mg, 0.1 mmol) and toluene (2 mL) under nitrogen atmosphere. The reaction mixture was heated at 800C for 48 hours. It was then allowed to cool to room temperature, taken up in ether/ethyl acetate, filtered and concentrated. The crude material was subjected to column chromatography on silica gel (Biotage, eluent hexanes/ethyl acetate 70/30) to afford Compound 13 as a yellow solid. LCMS m/z (%) = 358 (M+H 79Br, 100), 360 (M+H 81Br, 98).
Reference: [1]Current Patent Assignee: PFIZER INC - WO2006/60762, 2006, A2 Location in patent: Page/Page column 72
99% With caesium carbonate In water; N,N-dimethyl-formamide at 20℃; Inert atmosphere; General procedure for Suzuki cross coupling reaction General procedure: The Suzuki coupling reactions were carried out in a test tube (13 mm) using an organic synthesizer. Aryl iodides, bromides and chlorides (0.1 mmol) base (150 mol%), arylboronic acid (0.15 mmol) and Pd catalysts 3-5 atom% were placed in a test tube. The argon gas was supplied from the balloon with argon exchange 2 times without degassing. Solvent was added and stirred at 1000 rpm at specified temperature for the desired time. Completion of the reaction was monitored by TLC. After completion, the reaction was cooled and quenched by 1M HCl, extract with EtOAc. The organic layer was evaporated, dried and the yields were reported as NMR or isolated yield after purification by silica gel column chromatography (eluted with EtOAc/Hexane). The products were confirmed by 1H NMR spectra and mass comparing with the pure, commercially available compounds and reported NMR in the literature which exactly matched with the reported values.1-18
95% With sodium carbonate In 1-methyl-pyrrolidin-2-one at 100℃; for 8h; Inert atmosphere;
84% With potassium fluoride In toluene at 80℃; for 3.5h;
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; N,N-dimethyl-formamide at 110℃; Inert atmosphere; Sealed tube; General procedure: To a solution of 4-Methylphenylboronic acid (2.8g,21mmol) in DMF/water (v/v, 1:1) was added 1-bromo-4-iodobenzene (4g, 14mmol) , Tetrakis (triphenylphosphine)palladium (0.8g, 0.7mmol) and K2CO3 (5.8g, 42mmol), themixture was stirred at 110oC in a sealed tube under N2 over night. The reaction mixture was cooled and poured into an ice-wate rmixture solution, filtering to get solid material. The residue was purified by column chromatography on silica gel (petroleum ether) to yield the title compound
Reference: [1]Karanjit, Sangita; Kashihara, Masaya; Nakayama, Atsushi; Shrestha, Lok Kumar; Ariga, Katsuhiko; Namba, Kosuke [Tetrahedron, 2018, vol. 74, # 9, p. 948 - 954]
[2]Nikitin, Oleg M.; Polyakova, Olga V.; Sazonov, Petr K.; Yakimansky, Alexander V.; Goikhman, Mikhail Ya.; Podeshvo, Irina V.; Magdesieva, Tatiana V. [New Journal of Chemistry, 2016, vol. 40, # 12, p. 10465 - 10473]
[3]Suzuki, Ken; Fontaine, Arnaud; Hori, Yoji; Kobayashi, Tohru [Synlett, 2007, # 20, p. 3206 - 3208]
[4]Ding, Yuyang; Mao, Liufeng; Xu, Dengfeng; Xie, Hui; Yang, Ling; Xu, Hongjiang; Geng, Wenjun; Gao, Yong; Xia, Chunguang; Zhang, Xiquan; Meng, Qingyi; Wu, Donghai; Zhao, Junling; Hu, Wenhui [Bioorganic and Medicinal Chemistry Letters, 2015, vol. 25, # 14, p. 2744 - 2748]
90% With palladium diacetate at 20℃; for 3h; Green chemistry;
82% With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In methanol; toluene for 12h; Reflux; Inert atmosphere; regiospecific reaction; 4.2.1. 4-Bromo-4'-methoxybiphenyl (4)23 The reaction was carried out by following the reflux-12 h procedure, using p-dibromobenzene (2, 0.50 g, 2.12 mmol), 4-methoxyphenyl boronic acid (3a, 0.22 g, 1.41 mmol), cesium carbonate (0.92 g, 2.82 mmol), Pd(PPh3)4 (0.13 g, 0.11 mmol), toluene (20 mL), and methanol (10 mL). Compound 4 was isolated by column chromatography (silica gel, cyclohexane/AcOEt 8/2) as a white solid (0.31 g, 82% yield), mp: 143-145 °C; 1H NMR (400 MHz, CDCl3) δ: 7.53 (dd, 4H, J=7.6, 8.8 Hz, ArH), 7.40 (d, 2H, J=8.3 Hz, ArH), 6.97 (d, 2H, J=8.8 Hz, ArH), 3.84 (s, 3H, OCH3) ppm; MS m/z (%): 264 (M+, 0.2), 262 (0.2), 184 (100), 169 (47), 152 (5).
80% Stage #1: 1.4-dibromobenzene With 3,3'-(pyridine-2,6-diylbis(1H-imidazole-3-ium-1,3-diyl))bis(propane-1-sulfonate); palladium diacetate; potassium carbonate In water; acetonitrile at 30℃; for 0.166667h; Inert atmosphere; Schlenk technique; Stage #2: 4-methoxyphenylboronic acid In water; acetonitrile at 20℃; for 12h; Inert atmosphere; Schlenk technique;
80% With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In methanol; toluene at 100℃; for 16h; Inert atmosphere; 18.A Step A: Step A: 4-bromo-4'-methoxy-1,1'-biphenyl To a solution of (4-methoxyphenyl)boronic acid (5 g, 32.9 mmol) in toluene/MeOH (200 mL/100 mL) was added 1,4-dibromobenzene (11.6 g, 49.4 mmol), Pd(PPh3)4 (1.9 g, 1.65 mmol) and Cs2CO3 (21.4 g, 65.8 mmol). The resulting solution was stirred at 100° C. for 16 hours under N2 atmosphere. TLC showed the reaction was completed. After cooled to room temperature, the reaction mixture was diluted with 50 mL of EA, washed with water, brine. The organic phase was dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by chromatography column to afford 4-bromo-4'-methoxy-1,1'-biphenyl (7.0 g, 80% yield). LCMS (ES+): m/z 263.1 [M+H]+.
80% With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In methanol; toluene at 100℃; for 16h; Inert atmosphere; A Step A: 4-bromo-4'-methoxy-1,1'-biphenyl To a solution of (4-methoxyphenyl)boronic acid (5 g, 32.9 mmol) in toluene/ MeOH (200 mL/100 mL) was added 1,4-dibromobenzene (11.6 g, 49.4 mmol), Pd(PPh3)4 (1.9 g, 1.65 mmol) and Cs2CO3 (21.4 g, 65.8 mmol). The resulting solution was stirred at 100 °C for 16 hours under N2 atmosphere. TLC showed the reaction was completed. After cooled to room temperature, the reaction mixture was diluted with 50 mL of EA, washed with water, brine. The organic phase was dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by chromatography column to afford 4-bromo-4'-methoxy-1,1'-biphenyl (7.0 g, 80% yield). LCMS (ES+): m/z 263.1 [M+H]+.
69% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In toluene at 90 - 100℃; for 14h; Inert atmosphere;
67% With potassium hydroxide In water at 60℃; for 10h;
34% With palladium diacetate; caesium carbonate; triphenylphosphine In toluene at 110℃; for 16h; Inert atmosphere;
Stage #1: 1.4-dibromobenzene; 4-methoxyphenylboronic acid With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran for 0.25h; Inert atmosphere; Stage #2: With sodium carbonate In tetrahydrofuran; 1,2-dimethoxyethane; water at 70℃; for 12h; Inert atmosphere; Synthesis of 25 Under an argon atmosphere 19 (2.0 g, 13.1 mmol), 1,4-dibromobenzene (6.2 g, 26.3 mmol, 2 eq.) and Pd(PPh3)4 (0.23 g, 0.2 mmol) were dissolved in dry THF (44 mL, 0.3 M). After stirring for 15 min, a solution of Na2CO3 (5.58 g, 52.6 mmol) in H2O (14 mL, 60 eq.) was added to the reaction mixture. And then some droplets of ethylene glycol were added to the mixture and heated to 70 °C for 12 h. After cooling to room temperature, the mixture was filtered through celite using ethyl acetate. The resulting organic layer was washed with saturated aqueous solution of ammonium chloride and brine. The combined organic layers were dried over anhydrous MgSO4 and evaporated under reduced pressure. The crude product was suspended in boiling ethanol (60 mL) and filtered while being hot. (Gray filter cake was obtained). Residual filtrate was crystallized by cold EtOH.
Reference: [1]Boruah, Preeti Rekha; Ali, Abdul Aziz; Chetia, Mitali; Saikia, Bishwajit; Sarma, Diganta [Chemical Communications, 2015, vol. 51, # 57, p. 11489 - 11492]
[2]Location in patent: experimental part Guillén, Elena; Hierrezuelo, Jesús; Martínez-Mallorquín, Rocio; López-Romero, J. Manuel; Rico, Rodrigo [Tetrahedron, 2011, vol. 67, # 14, p. 2555 - 2561]
[3]Prajapati; Schulzke; Kindermann; Kapdi [RSC Advances, 2015, vol. 5, # 65, p. 53073 - 53085]
[4]Current Patent Assignee: ARVINAS; YALE UNIVERSITY - US2018/179183, 2018, A1 Location in patent: Paragraph 1606
[5]Current Patent Assignee: ARVINAS; YALE UNIVERSITY - WO2020/51564, 2020, A1 Location in patent: Paragraph 0909; 0910
[6]Moorthy, Jarugu Narasimha; Koner, Apurba L.; Samanta, Subhas; Roy, Ankur; Nau, Werner M. [Chemistry - A European Journal, 2009, vol. 15, # 17, p. 4289 - 4300]
[7]Dey, Deepa; Bhattacharya, Tamalika; Majumdar, Biju; Mandani, Sonam; Sharma, Bhagwati; Sarma, Tridib K. [Dalton Transactions, 2013, vol. 42, # 38, p. 13821 - 13825]
[8]Mills, L. Reginald; Graham, Joshua M.; Patel, Purvish; Rousseaux, Sophie A. L. [Journal of the American Chemical Society, 2019, vol. 141, # 49, p. 19257 - 19262]
[9]Kim, Nam-Kyun; Sogawa, Hiromitsu; Takata, Toshikazu [Tetrahedron Letters, 2020, vol. 61, # 23]
39% Stage #1: 4-bromo-4'-methoxylbiphenyl With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: 1-[1H-imidazol-4(5)-yl]-2-methylpropan-1-one In tetrahydrofuran; hexane at -78 - 20℃; Stage #3: With water; ammonium chloride In tetrahydrofuran; hexane 4.1. General procedure for method A and 1-[1,1'-biphenyl]-3-yl-1-(1H-imidazol-4-yl)-2-methyl-1-propanol (5) General procedure: n-BuLi in hexane (1.6 M; 6.4 mL, 10.2 mmol) was added to a cooled (-78 °C) solution of 2a (2.11 g, 9.05 mmol) in THF (30 mL) and the mixture was stirred at -78 °C for 1 h. A solution of 4 (400 mg, 2.89 mmol) in THF (10 mL) was added to the mixture and the solution was allowed to warm to rt. The reaction was quenched with aqueous NH4Cl solution and the aqueous phase was extracted with AcOEt. The extract was dried over MgSO4 and concentrated under reduced pressure. The residue was chromatographed on silica gel (CH2Cl2/MeOH = 20:1) and recrystallized from AcOEt-hexane to give 5 (450 mg, 1.54 mmol, 53%) as a colorless powder.
Reference: [1]Location in patent: experimental part Kaku, Tomohiro; Tsujimoto, Saori; Matsunaga, Nobuyuki; Tanaka, Toshimasa; Hara, Takahito; Yamaoka, Masuo; Kusaka, Masami; Tasaka, Akihiro [Bioorganic and Medicinal Chemistry, 2011, vol. 19, # 7, p. 2428 - 2442]
97% With potassium carbonate; palladium dichloride In ethanol; water at 20℃; for 0.5h; General procedure for the Suzuki reaction of aryl bromides with arylboronic acids General procedure: A mixture of aryl bromide (0.5 mmol), arylboronic acid (0.75 mmol), PdCl2 (0.0025 mmol, 0.44 mg), K2CO3 (1 mmol) was stirred in distilled water (2 mL) and ethonal (2 mL) at room temperature in air for the indicated time. After the completion of the reaction, the mixture was quenched by brine (15 mL), extracted with diethyl ether (4×10 mL), dried by anhydrous MgSO4, concentrated under vacuum and the product was afforded by column chromatography on silica gel (200-300 mesh) eluted with petroleum ether and ethyl acetate.
94% With potassium carbonate In ethyl acetate at 90℃; for 1.5h;
87% With C12H12Cl2N4O2Pd; caesium carbonate In water at 60℃; for 4h; General procedure for the Reaction of Arylboronic Acids and Halobenzenes General procedure: In an oven dried 10 mL round bottom flask were added arylboronic acid 1 (1.0 mmol), halobenzene 2 (1.0 mmol), Cs2CO3 (0.5 equiv) and catalyst C4 (1.0 mol%) in water (1mL). The reaction mixture was allowed to stir at 60 oC for completion. After completion of reaction (monitored by TLC) the crude residue was extracted into in ethylacetate (10 mL x 3) and dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure. The crude mixture was separated using silica-gel column chromatography by eluting with ethylacetate/hexanes.
7 %Spectr. With C16H28Cl2N4O2Pd; potassium carbonate In methanol; carbon dioxide at 120℃; for 1h; Supercritical conditions;
Reference: [1]Qiu, Jun; Wang, Limin; Liu, Mingtao; Shen, Qiang; Tang, Jun [Tetrahedron Letters, 2011, vol. 52, # 48, p. 6489 - 6491]
[2]Han, Yi; Di, Jia-Qi; Zhao, Ai-Dong; Zhang, Zhan-Hui [Applied Organometallic Chemistry, 2019, vol. 33, # 10]
[3]Thunga, Sanjeeva; Poshala, Soumya; Anugu, Naveenkumar; Konakanchi, Ramaiah; Vanaparthi, Satheesh; Kokatla, Hari Prasad [Tetrahedron Letters, 2019, vol. 60, # 31, p. 2046 - 2048]
[4]Location in patent: experimental part Fernandes, Ricardo R.; Lasri, Jamal; DaSilva, M. Fatima C. Guedes; Palavra, Antonio M. F.; Dasilva, Jose A. L.; Dasilva, Joao J. R. Frausto; Pombeiro, Armando J. L. [Advanced Synthesis and Catalysis, 2011, vol. 353, # 7, p. 1153 - 1160]
72% With bis-triphenylphosphine-palladium(II) chloride; sodium dodecyl-sulfate; potassium carbonate; p-toluenesulfonyl chloride In water at 60℃; Typical procedure for Pd-catalyzed Suzuki cross-coupling of arylhydrazines with aryl boronic acids General procedure: A mixture of arylhydrazine 1 (0.24mmol, 1.2equiv.), aryl boronic acid 2 (0.2 mmol), K2CO3(0.6 mmol, 3.0 equiv.), p-toluenesulfonylchloride (0.24 mmol, 1.2 equiv.), sodium dodecyl sulfate (0.02 mmol, 10 mol %), and PdCl2(PPh3)2(0.01 mmol, 5 mol %) was stirred at 60 °C in water (2.0 mL) for 4-8 h under air.After completion of the reaction (indicated by TLC), the mixture was quenched with saturatedNaCl solution, extracted by EtOAc,and dried with Na2SO4. The crude product was purified by flash columnchromatography to provide the corresponding product 3.
Reference: [1]Liu, Jin-Biao; Zhou, He-Ping; Peng, Yi-Yuan [Tetrahedron Letters, 2014, vol. 55, # 17, p. 2872 - 2875]
32 %Chromat. With N-Bromosuccinimide; [bis(acetoxy)iodo]benzene; nickel dibromide In water-d2 at 25℃; for 24h; Sealed tube; Inert atmosphere; 2.3. Standard procedure for catalytic bromination General procedure: To 2 mL CF3COOH (or D2O), 0.25 mmol substrate, 0.5 mmol oxidizing agent, 0.375 mmol NBS and 5 mol% catalyst were added. The reagents were taken in a specially designed tube (10 mL), were purged with N2 gas, and sealed; the mixture was stirred for 24 h at room temperature. Next, the volatiles were removed under reduced pressure. The brominated products were analyzed by 1HNMR spectroscopy and the yields were calculated by GC/MS using dodecane as an internal standard.
32.0 %Chromat. With N-Bromosuccinimide; [bis(acetoxy)iodo]benzene; nickel dibromide In water-d2 at 20℃; for 24h; Inert atmosphere; Sealed tube;
Reference: [1]Bhattacharya, Moumita; Cluff, David B.; Das, Siddhartha [Inorganica Chimica Acta, 2014, vol. 423, # 1, p. 238 - 241]
[2]Bhattacharya, Moumita; Cluff, David B.; Das, Siddhartha [Inorganica Chimica Acta, 2014, vol. 423, # PA, p. 238 - 241]
(5-bromo-2-chlorophenyl)(4'-methoxy-[1, 1'-biphenyl]-4-yl)methanol [ No CAS ]
60% General procedure: To a cold (-78 oC) solution of 4-bromo-4'-methylbiphenyl 14d (2.5g, 10mmol) in THF (25mL) was added n-BuLi (2.5M in hexane; 4 mL, 10 mmol) and the mixture was stirredat -78 oC for 1 h. To the reaction mixture was added a solution of 10c(2.34 g, 11mmol) in THF (20 mL) and the mixture was stirred at -78 oCfor 3h. To the reaction mixture was added saturated ammonium chloride solutionand EtOAc, then the organic layer was separated and washed with brine, driedover Na2SO4, filtered and evaporated in vacuo. Theresulting residue was purified by column chromatography on silica gel(EtOAc/petroleum ether = 1:10) to give the title compound.
Reference: [1]Bioorganic and Medicinal Chemistry Letters,2015,vol. 25,p. 2744 - 2748
88% With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 1.5h; 2.4. General procedure for Suzuki-Miyaura cross-coupling General procedure: A round bottom flask (50 mL) equipped with condenser was chargedwith aryl halide (1.0 mmol), arylboronic acid (1.2 mmol), K2CO3(2 mmol), Pd(II)-AMP-CellAl2O3 (40 mg) and dimethyl formamide(DMF) (5 mL). The mixture was stirred in an oil bath at 80 °C. Uponcompletion of the reaction as monitored by thin layer chromatography(TLC) (petroleum ether:ethyl acetate, 95:0.5), the reaction mixture wasfiltered. The filtrate was extracted with ethyl acetate (3 × 5 mL). Thecombined organic layers were collected, dried over anhydrous Na2SO4,and concentrated in vacuum to afford the crude products. These productswere purified by silica gel column chromatography (Ether /EtOAc = 9:1 v/v).
83% With bis-triphenylphosphine-palladium(II) chloride; Aliquat 336; potassium carbonate In tetrahydrofuran; water Reflux;
76% With sodium carbonate In water; toluene at 100℃; for 12h; Inert atmosphere; 1.1 Step 1: Synthesis of 4-bromo-4'-methoxy-1,1'-biphenyl (21): To a mixture of compound 19 (200 mg, 0.85 mmol)and compound 20 (257 mg, 1.28 mmol)in toluene- water (9: 1)(35 mL)was added Na2CO3 (181 mg, 1.70 mmol)and the reaction mixture was degassed with N2 for 20 min. PdCl2(dppf complex (60 mg, 0.08 mmol)was added and the reaction mixture was heated to 100 °C for 12 h. After completion of the reaction, the mixture was filtered through a Celite pad, filtrate was concentrated and purified by silica gel column chromatography [gradient elution with EtOAc: Hexane (10:90)] to afford compound 21 (200 mg, 76%). 1H NMR (400 MHz, CD2Cl2): d 7.51 (dd, J= 17.5, 7.0, 2.2 Hz, 4H), 7.41 (dd, J = 8.7, 2.1 Hz, 2H), 6.97 (dd, J= 8.7, 2.1 Hz, 2H), 3.85 (s, 3H).
Reference: [1]Mhaldar, Pradeep; Pore, Dattaprasad; Rashinkar, Gajanan; Vibhute, Sandip [Reactive and Functional Polymers, 2020, vol. 152]
[2]Sen, Choong Ping; Valiyaveettil, Suresh [RSC Advances, 2016, vol. 6, # 97, p. 95137 - 95148]
[3]Current Patent Assignee: SRX CARDIO LLC - WO2020/252383, 2020, A2 Location in patent: Paragraph 00232; 00248
Reference: [1]RSC Advances,2016,vol. 6,p. 95137 - 95148
58% Stage #1: 4-bromo-4'-methoxylbiphenyl With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran; hexane at -78 - 5℃; 18.B Step B: Step B: (4'-methoxy-[1,1'-biphenyl]-4-yl)boronic acid To a solution of 4-bromo-4'-methoxy-1,1'-biphenyl (2 g, 7.63 mmol) in dry THF (30 mL) was added n-BuLi (9.2 ml, 22.9 mmol, 2.5 M in hexane) dropwise at -78° C. under N2 atmosphere. 1 hour later, (CH3O)3B (2.38 g, 22.9 mmol) was added dropwise at -78° C. The resulting solution was stirred for 1 hour at -78° C. and overnight at 5° C. After quenched with saturated NH4Cl solution, the mixture was extracted with EA (30 mL*2.) The combined organic layer was dried over anhydrous sodium sulfate. The residue was purified by chromatography column to afford (4'-methoxy-[1,1'-biphenyl]-4-yl)boronic acid (1.0 g, 58% yield). 1H NMR (400 MHz, DMSO-d6): δ 8.06 (s, 2H), 7.84 (d, J=7.6 Hz, 2H), 7.63 (d, J=7.6 Hz, 2H), 7.58 (d, J=7.6 Hz, 2H), 7.02 (d, J=7.6 Hz, 2H), 3.80 (s, 3H).
58% Stage #1: 4-bromo-4'-methoxylbiphenyl With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran; hexane at -78 - 5℃; B Step B: (4'-methoxy-[ biphenyl]-4-yl)boronic acid To a solution of 4-bromo-4'-methoxy-1,1'-biphenyl (2 g, 7.63 mmol) in dry THF (30 mL) was added n-BuLi (9.2 ml, 22.9 mmol, 2.5 M in hexane) dropwise at -78 oC under N2 atmosphere.1 hour later, (CH3O)3B (2.38 g, 22.9 mmol) was added dropwise at -78 oC. The resulting solution was stirred for 1 hour at -78 oC and overnight at 5 °C. After quenched with saturated NH4Cl solution, the mixture was extracted with EA (30 mL x 2.) The combined organic layer was dried over anhydrous sodium sulfate. The residue was purified by (2081) chromatography column to afford (4'-methoxy-[1,1'-biphenyl]-4-yl)boronic acid (1.0 g, 58% yield). 1H NMR (400 MHz, DMSO-d6): d 8.06 (s, 2H), 7.84 (d, J = 7.6 Hz, 2H), 7.63 (d, J = 7.6 Hz, 2H), 7.58 (d, J = 7.6 Hz, 2H), 7.02 (d, J = 7.6 Hz, 2H), 3.80 (s, 3H).
Reference: [1]Current Patent Assignee: ARVINAS; YALE UNIVERSITY - US2018/179183, 2018, A1 Location in patent: Paragraph 1608
91% Stage #1: o-benzenedisulfonimide; 4-bromo-aniline With acetic acid at 0 - 5℃; for 0.166667h; Inert atmosphere; Stage #2: With isopentyl nitrite for 0.166667h; Inert atmosphere; Stage #3: 4-methoxyphenylboronic acid With bis[(trifluoromethanesulfonyl)imidate]-2-(dicyclohexyl(2',6'-dimethoxybiphenyl))phosphine gold(I); caesium carbonate In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; chemoselective reaction; 3.19 4.3 4-Methoxybiphenyl (4a): representative procedure for the Au catalysed Suzuki-Miyaura couplings General procedure: In a oven-dried flask and under nitrogen flow, benzenediazonium o-benzenedisulfonimide (1a, 161mg, 0.5mmol) was added to a suspension of 4-methoxyphenylboronic acid (3a, 91mg, 0.6mmol), [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) (2:1) toluene adduct (39mg, 0.025mmol, 5mol%), Cs2CO3 (325mg, 1mmol) in THF (5mL). The resulting mixture was stirred at room temperature for 2h; the completion of the reaction was confirmed by the absence of azo coupling with 2-naphthol. Then, the reaction mixture was poured into diethyl ether/water (100mL, 1:1). The aqueous layer was separated and extracted with diethyl ether (50mL). The combined organic extracts were washed with water (50mL), dried with Na2SO4 and evaporated under reduced pressure. GC-MS analyses of the crude residue showed 4-methoxybiphenyl (4a), MS (EI): m/z 184 (M+) as the major product, besides traces of biphenyl, MS (EI): m/z 154 (M+), 4,4'-dimethoxybiphenyl, MS (EI): m/z 214 (M+), N-phenyl-o-benzenedisulfonimide, MS (EI): m/z 295 (M+). The crude residue was purified on a short column, eluting with petroleum ether/diethyl ether (9:1). The only isolated product was the title compound (4a, 81mg, 88% yield).
Reference: [1]Barbero, Margherita; Dughera, Stefano [Tetrahedron, 2018, vol. 74, # 39, p. 5758 - 5769]
6-(4'-methoxy-[1,1'-biphenyl]-4-yl)benzo[c]chromen-5-ium perchlorate [ No CAS ]
43% Stage #1: 4-bromo-4'-methoxylbiphenyl With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1.5h; Inert atmosphere; Stage #2: 6H-benzo[c]chromen-6-one In tetrahydrofuran; hexane at -78 - 20℃; for 2h; Inert atmosphere; Stage #3: With perchloric acid; acetic anhydride In diethyl ether; water at 0℃; 4.4. 6-(40-Methoxy-[1,10-biphenyl]-4-yl)benzo[c]chromen-5-iumperchlorate (15) 4-bromo-4'-methoxybiphenyl 6 (0.671 g, 2.55 mmol) was dissolved in 10 mL of anhydrous THF in an oven dried round bottom flask. The solution was cooled to 78 C in a dry ice/acetone bath and sparged with Ar for 45 min. 1.6 M n-BuLi in hexane (1.70 mL,2.72 mmol) was added dropwise via syringe and the reaction was stirred for 1.5 h at 78 C. During this time 6H-benzo[c]chromen-6-one 9 (0.500 g, 2.55 mmol) was dissolved in 10 mL of anhydrous THF in a separate oven dried round bottom flask. The solution was cooled to 78 C in a dry ice/acetone bath and sparged with Ar for 30 min. The aryllithium solution was transferred to the solution containing 9 at 78 C via cannula under Ar pressure. The cooling bath was removed, and the reaction was allowed to stir for 2 h. 50 mL of sat. NH4Cl was added to the reaction and subsequently extracted 3x with 25 mL of Et2O. The combined organics were dried with MgSO4, filtered, and concentrated under reduced pressure. The crude product was dissolved in 25 mL of diethyl ether and cooled to 0 C in an ice bath and stirred very rapidly. A chilled (0 C) solution of 70% perchloric acid in acetic anhydride (1:3 by volume) was slowly added drop-wise to the stirring ethereal solution until a colored precipitate formed. The crude product was filtered and recrystallized in glacial acetic acid to yield a red-orange powder (0.508 g, 43%). mp 270e271 C. 1H NMR (400 MHz, CDCl3/CF3CO2D): d 8.90 (d, J 8.5 Hz, 1H), 8.86 (d, J 8.5 Hz, 1H), 8.76 (dd,J 8.3 Hz, J 1.5 Hz, 1H), 8.59 (t, J 7.9 Hz, 1H), 8.36 (d, J 8.5 Hz,2H), 8.27 (dd, J 8.4 Hz, J 1.1 Hz, 1H), 8.17 (t, J 8.3 Hz, 1H), 8.12(td, J 7.9 Hz, J 1.5 Hz, 1H), 8.07-8.01 (m, 3H), 7.77 (d, J 9.0 Hz,2H), 7.12 (d, J 8.8 Hz, 2H), 3.95 (s, 3H). 13C NMR (100 MHz, CDCl3/CF3CO2D): d 183.7, 160.6, 151.6, 150.2, 143.9, 139.7, 136.2, 134.9,134.3,132.1, 131.2, 131.0,129.2,128.2, 127.3, 124.1,124.0, 121.5, 120.5,119.8, 115.3, 55.9. IR (ATR) nmax: 1592, 1483, 1078 cm1. HRMS (ESI)m/z calcd for C26H19O2 [M] 363.1385, found 363.1373.
Reference: [1]Meyer, Samantha M.; Charlesworth-Seiler, Eva M.; Patrow, Joel G.; Kitzrow, Jonathan P.; Gerlach, Deidra L.; Reinheimer, Eric W.; Dahl, Bart J. [Tetrahedron, 2020, vol. 76, # 23]
9-(4'-methoxy-[1,1'-biphenyl]-4-yl)xanthylium perchlorate [ No CAS ]
47% Stage #1: 4-bromo-4'-methoxylbiphenyl With magnesium; ethylene dibromide In tetrahydrofuran Reflux; Inert atmosphere; Stage #2: xanth-9-one In tetrahydrofuran at 0 - 20℃; for 2h; Inert atmosphere; Stage #3: With perchloric acid; acetic anhydride In diethyl ether; water at 0℃; for 0.5h; 4.10. 9-(40methoxy-[1,10-biphenyl]-4-yl)xanthylium perchlorate (24) Magnesium (0.132 g, 5.42 mmol) was placed into an oven-dried round bottom flask and flushed with Ar for 30 min while stirring. 4-Bromo-4'-methoxybiphenyl 6 (1.43 g, 5.42 mmol), anhydrous THF(8 mL), and 2 drops of 1,2-dibromoethane were then added. The reaction was heated to reflux, stirred for 30 min under Ar, and allowed to cool back to rt over 1 h. During this time xanthone 18 (0.532 g, 2.71 mmol) was dissolved in 16 mL of anhydrous THF in a separate oven dried round bottom flask. The flask was cooled to0 C with an ice bath and sparged for 30 min with Ar. The arylmagnesium bromide solution was transferred to the solution containing 18 at 0 C via cannula under Ar pressure. The cooling bath was removed, and the reaction was stirred for 2 h. 50 mL of sat. NaHCO3 was added to the reaction and subsequently extracted 3x with 100 mL of CH2Cl2. The combined organics were washed dried with Na2SO4, filtered, and concentrated under reduced pressure. The crude intermediate was purified via column chromatography using gradient elution (5% EtOAc in hexane/50% EtOAc in hexane) but not characterized further. The purified intermediate was dissolved in 10 mL of diethyl ether and 70% aq. HClO4 was added dropwise at rt until a colored precipitate formed. The reaction was allowed to stir for 30 min and filtered to yield a red solid. The solid was recrystallized in glacial acetic acid to yield small red needles (0.595 g, 47%). mp 230e231 C. 1H NMR (400 MHz, CDCl3/CF3CO2D): d 8.51 (ddd, J 8.6 Hz, J 7.0 Hz, J 1.2 Hz, 2H), 8.37 (d,J 8.8 Hz, 2H) 8.33 (dd, J 8.7 Hz, J 1.3 Hz, 2H), 8.01-7.94 (m, 4H),7.78 (d, J 8.1 Hz, 2H), 7.73 (d, J 8.8 Hz, 2H), 7.10 (d, J 8.8 Hz, 2H)3.94 (s, 3H). 13C NMR (100 MHz, CDCl3/CF3CO2D): d 174.9, 160.2,158.3, 145.7, 144.0, 132.0, 131.9, 131.4, 129.4, 128.7, 128.6, 127.3,123.5,120.0,114.8, 55.6. IR (ATR) nmax: 1596,1578,1083 cm1. HRMS(ESI) m/z calcd for C26H19O2 [M] 363.1385, found 363.1382.
69% With copper(l) iodide; trans-bis(triphenylphosphine)palladium dichloride; water; 1,8-diazabicyclo[5.4.0]undec-7-ene In benzene at 60℃; for 24h; Inert atmosphere; Darkness; 9 Synthesis of compound 12 Add 4-bromo-4-methoxybiphenyl (2.7g, 10.12mmol), DBU (9.2g, 60.43mmol), bistriphenylphosphine palladium dichloride (425mg) into a 100mL two-necked flask, cuprous iodide (191mg), under the protection of argon, ventilate three times, add benzene 40mL, add Trimethylsilylacetylene (0.71mL), water (70ul), Heat to 60°C for 24h in the dark. After the reaction, the reaction solution was cooled to room temperature, and the solvent was removed by rotary evaporation. Add dichloromethane to disperse, filter with suction, wash the residue with water several times, methanol washed to obtain a brown crude product, after recrystallization with a large amount of toluene, compound 12 was obtained as a white solid (1.4 g, 69%).
Reference: [1]Current Patent Assignee: DONGHUA UNIVERSITY - CN109456301, 2021, B Location in patent: Paragraph 0063-0066
C14H14O2Zn*MgBr*2LiCl [ No CAS ]
35% In 2-methyltetrahydrofuran; 1-methyl-pyrrolidin-2-one; at 80℃; for 0.5h;Glovebox; Microwave irradiation; Inert atmosphere; General procedure: In a glovebox, (het)arylpivalate 1 (0.2 mmol) and NMP (1.5 mL) were added to thediarylzinc 2 (0.3 mmol, prepared by mixing zinc bromide, lithium chloride, and the corresponding aryl magnesium bromidein 1.5 mL of THF) in a reaction tube. The reaction mixturewas then heated at 80 C for 0.5 h under MW irradiation.After completion of the reaction, the mixture was concentratedunder vacuum, and saturated NH4Cl added. The mixturewas extracted with CH2Cl2 several times. The combinedorganic layers were dried over anhydrous MgSO4, concentratedin vacuo, and the residue was purified by column chromatographyon silica gel to give the coupling product 3.
Reference: [1]Journal of Chemical Research,2021,vol. 45,p. 869 - 875
N-(4-fluoro-5-methoxy-2-nitrophenyl)-4'-methoxy[1,1'-biphenyl]-4-amine [ No CAS ]
26% With tris-(dibenzylideneacetone)dipalladium(0); sodium tertiary butoxide; dicyclohexyl[2',4',6'-tris(propan-2-yl)[1,1'-biphenyl]-2-yl]phosphane In toluene at 100℃; for 16h; 9.1 Step 1: N-(4-Fluoro-5-methoxy-2-nitrophenyl)-4'-methoxy-[1,1'-biphenyl]-4-amine. A mixture of 4-fluoro-5-methoxy-2-nitroaniline (155 mg, 0.84 mmol), 1-bromo-4-(4-methoxyphenyl)benzene (200 mg, 0.76 mmol), tris(dibenzylideneacetone)dipalladium(0) (35 mg, 0.04 mmol), XPhos (36 mg, 0.08 mmol), sodium tert-butoxide (146 mg, 1.52 mmol), and toluene (2 mL) was degassed with 2 vacuum/N2 cycles, stirred at 100 °C for 16 h, and then allowed to cool to rt. The mixture was diluted with EtOAc (15 mL) and water (10 mL). Celite was added, and the mixture was filtered through Celite. The filter cake was washed with EtOAc (10 mL). The organic layer was washed with brine (10 mL), dried (Na2SO4), filtered, concentrated, and then purified by silica gel chromatography (0-15% EtOAc in hexanes) to give N-(4-fluoro-5-methoxy-2-nitrophenyl)-4'-methoxy-[1,1'-biphenyl]-4-amine (73 mg, 26%) as an orange solid. 1H NMR (400 MHz, DMSO-d6): δ 9.74 (s, 1H), 8.02 (d, J = 11.9 Hz, 1H), 7.67 (m, 4H), 7.48 (d, J = 8.6 Hz, 2H), 7.04 (d, J = 8.8 Hz, 2H), 6.85 (d, J = 7.8 Hz, 1H), 3.83-3.81 (m, 3H), 3.81-3.80 (m, 3H); LCMS: 369.2 [M+H]+.
Reference: [1]Current Patent Assignee: METACRINE INC - WO2022/72491, 2022, A1 Location in patent: Paragraph 00417
[2]Current Patent Assignee: METACRINE INC - WO2022/72491, 2022, A1 Location in patent: Paragraph 00417
4'-Bromo-3-Methoxy-1,1'-biphenyl
4,4'-Bis(3-bromophenoxy)-1,1'-biphenyl
5-Bromo-4'-methoxy-[1,1'-biphenyl]-3-ol


Last chance! This book is out-of-print and we don't have many copies left. Get it while you can!
Matt Tavares s luminous illustrations and Stephen Mitchell s wry text transform this classic Grimms fairy tale into a splendid edition to treasure.
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Iron Hans is nine feet tall and as brown as rust, with hair to his knees. He is cursed, a terror to all, until a young prince finds the courage to befriend him. But when the boy betrays Iron Hans s trust, he must make his way in the world alone, penniless and unknown save for a little help from a certain forgiving wild man. Stephen Mitchell s deft retelling and Matt Tavares s elegant illustrations gracefully render this timeless Grimms tale about pride and humility, wealth and poverty, and the importance of doing good, whether servant or prince, wild man or king."


Real-time Network and Monitoring Manager and Pacific Islands Geospatial Manager in AllTerra New Zealand, Warren Eade, is in Samoa to showcase the new technology that they have in the market and how it can benefit our country.
Mr. Eade was one of the presenters at the Youth Co:Lab conference at the T.A.T.T.E. Building last week.
The New Zealand Company is in partnership with the Samoa Stationery and Books (S.S.A.B.) and it was through S.S.A.B. that they were able to participate in the conference.
Speaking to the Samoa Observer, Mr. Eade said his role is within the Trimble Product portfolio.
"While the conference evolved around the digital Pacific, my role is actually within the Trimble Product portfolio, which is actually bringing digital and spatial together," he said.
"Spatial simply means location so all of our lives we do activities, we own properties, we have friends and families that are scattered around the place and all of that is actually location.
"And we try to look at the fact that in countries where there's no addressing system, I can't say go to number 12 of such and such street, we will need to do a bit of activity and ask what is that location and how do I communicate this to people that have never been there.
"This is where the 'Trimble Product' comes in. It provides spatial information and it has a coordinate, this is a coordinate where we don't need an address because it has a fixed position.
Moreover, he said it is a useful product to government organizations in locating their assets.
"Take organisations like Water Authority and Electric Power Corporation, they have millions and millions of dollars, assets with all those power poles and powerline and water meters and pipes, they need to know where they are," he said.
"They need to maintain them and replace them when things go wrong, and again if they don't have good records of where their assets are, they could spend a lot of money relocating them or they will even have to dig up a road to find them or dig up a foot path or they will even have to dig up someone else's property in trying to find them, but find out that what they are looking for is actually on the other side of the road.
"So Trimble will be helping these people get smart about how they can start locating their assets so that they can maintain them and can reduce the amount of cost they spend on obviously the maintenance of finding them or repaired price.
"It also enables government to locate assets of new road, bridge, hospital or a school these are government assets but they still operate and locate construction of roads which are highly important.
Asked if a country such as Samoa can benefit from this new technology Mr. Eade, said yes.
"Every country is going to benefit, it's just more of a speed in which they can adopt," he said.
"I've been travelling the Pacific region for over 10 years, so I've experienced change at a time and one of the big things that's highlighted in Samoa now is the fact that you've got the second major fiber cable coming into the country.
"This means Samoa is going to have 800 percent increase in speeded capacity on their telecommunications.
"That actually opens up a whole new world because before everything had to be posted locally we had to do our own data, we had to get our own desktops and every organization needed to run their own I.T. infrastructure, which came at a phenomenal cost.
"However, making this connectivity now more affordable and a lot more capacity it actually starts to open up, but best of all it's moving towards which that whole cloud space is, so literally think of it like a buffet meal.
"You only end up paying on what you use, you don't have to pay for this huge capacity because one day you might need it but now I can simply go to a cloud and say I need this much today, but tomorrow I will get this much so it becomes very simple.
"So Samoa is at a cutting edge point because other countries around the world and bear in mind I do come from New Zealand we get caught up in some of our own technology that's very hard to move away from.
"We have a lot of destructions that's been in the ground for so many years, which in many ways prevented us to make a giant leap forward and it wasn't until the Government implemented broadband rolled out everywhere that enabled us to take that giant step forward.
"Countries like Samoa, Fiji, Tonga and so forth haven't had the same impact and therefore you can actually make a quantum jump much easier so you can jump into 4G straight away and you will probably be the first country to even get 5G.
"So being small and remote is not always a bad thing because you don't get some of that old legacy issues that some other countries get.


The Echo Chamber's latest episode looks at disruption of the RFP process and also how brands can do thought-leadership better.
In the latest Echo Chamber episode, the head of marketing servies for Globality Gabrielle Tenaglia joins to talk about the platform that brings together small and mid-sized firms with brands — exploring various RFP pitfalls that the platform seeks to mitigate. In the second part of the show, March Communications VP Meredith Eaton comes on to examine the state of thought-leadership campaigns — who's doing them well? What does the term even mean today?


EHL – Where to watch?
13th April 2017: The EHL KO16 will be broadcast live by a variety of different outlets around the world, showcasing the world's best club hockey competition. Here's where you can watch every game live!
Next#FridayFocus – 2016 Club of the Year Winners: SG Rotation Prenzlauer Berg and Grove Menzieshill HC!


The presidential candidate of the Peoples Democratic Party (PDP), Atiku Abubakar had condemned and accused President Muhammadu Buhari of being a dictator over the suspension of the Chief Justice of Nigeria, Walter Onnoghen.
"The fact that the unlawful suspension of Chief Justice Walter Onnoghen was announced just as it became public knowledge that the CJN was constituting the election petition tribunals is not lost on discerning Nigerians and the international community. This act of desperation is geared towards affecting the outcome of the 2019 Presidential elections.
READ Malnutrition threatens learning outcomes of children in Nigeria's Northeast.