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Presented for your consideration, below are a number of linking-related comments, thoughts, ideas and other notes that I believe you'll find thought-provoking, interesting or, at least, somewhat helpful. Bittersweet Vindication..? On April 30 of 2007, almost exactly seven years ago today, I… . About SEO, PPC, SEM, Search Engines & Search Marketing
searchengineland.com - 11 months ago +Bookmark


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Tourism is defined as the activity of touring, especially for pleasure. Examples of tourism include visiting the Grand Canyon, traveling to a foreign country or going on an Alaskan cruise. People who are engaging in tourism are known as "tourists."
The economies of many states rely on tourism. Most states have a department devoted to tourism to promote their state and encourage people to travel there. These tourism departments direct visitors to popular attractions and events in each state, along with the best places to dine. They also assist people in finding suitable accommodations, from condominium rentals to rustic campgrounds.
Individuals have practiced medical tourism for thousands of years. In ancient Greece, pilgrims traveled all over the Mediterranean to the healing god, Asklepios, at Epidaurus. In
tourism is the activities of persons travailing to and staying in places outside their usual environment for not more than one conductive year. When people visit new places.
and how they have pulled off a website with absolutely breath-taking details. Below are few screenshots from older years. Just head over to Tennessee Tourism website would get updated
food. pretty things, awsome people, ugly flower shirts.

subset: commoncrawl


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Any questions? I am unable to find beef cheeks – have tried Whole Foods as well as two local butcher shops. No luck.
by MARY on November 26, 2012 in problems and questions
Post Author
This post was written by MARY who has written 107 posts on French Fridays with Dorie.
9 Responses to "P&Q – BEEF CHEEK DAUBE"
I couldn't get beef cheeks, so I used chuck roast – and doubled the carrots. I was told this was the best "pot roast" I have made. It was even better as leftovers.
(I might possibly have been chided for swiping two cups of someone's Malbec to use in the stew…Hey, if it's good enough for drinking, then it's good enough for cooking, right?)
Mardi (eat. live. travel. write.) November 27, 2012 at 2:54 AM #
I used stewing beef too – was too rushed the weekend I made this (and all the other FFWD recipes) to head out in search of the cheeks. It was SO good – odd for sure and hard to make it look pretty but so delicious. And of course decent wine helps ;)
Bakeawaywithme November 27, 2012 at 4:39 PM #
I'm also using chuck roast! I called 3 butchers in my area and they said they don't carry it and would not be able to get it for me. That made it easy!!
Today I purchased my chuck roast – felt defeated by the beef cheek search. It's something about having to be a store/shop that butchers the entire cow on premises which I understand most grocery stores and butcher shops no longer do. Cowards!
Also was feeling "cheeky" so went to my wine store and bought a bottle of good red wine – enough to pour in the pot and into my mouth.
I opened a fantastic cab, used the 2 cups and finished off the rest while it was cooking. When I was done I didn't much care if it was beef cheek, chuck, or tuna fish. Tasted great!
lizzydo November 30, 2012 at 5:01 AM #
Bakeawaywithme November 30, 2012 at 6:12 AM #
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Vote for February Recipes (Choose 3) -- Poll closes 1/28/15
- Vanilla-Butter-Braised Lobster (p324) (68%, 13 Votes)
- Riviera Fish Soup (p92) (58%, 11 Votes)
- Cabbage and Foie Gras Bundles (p193) (47%, 9 Votes)
- Chicken Couscous (p214) (47%, 9 Votes)
- Veal Marengo (p264) (47%, 9 Votes)
- Cheesecake Tart (p469) (32%, 6 Votes)
Total Voters: 19
Recipe Schedule
February 6, 2015: Winter Ceviche (p177)
February 13, 2015: Chicken Couscous (p214)
February 20, 2015: Vanilla-Butter-Braised Lobster (p324)
February 27, 2015: Riviera Fish Soup (p92)
March 6, 2015: Cabbage and Foie Gras Bundles (p193)
March 13, 2015: Veal Marengo (p264)
March 20, 2015: Côte d'Azur Cure-all Soup (p70)
March 27, 2015: Next-day Beef Salad (p260)


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Helms: State's daily oil production will double by '17
North Dakota's daily oil production will double to 1.6 million barrels by 2017, Department of Mineral Resources Director Lynn Helms said in a taped address to oil county and industry folks Thursday.
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NOV ASEP Elmar, a global market leader in the design and manufacture of wireline intervention equipment, has announced the successful completion of the first field operation for its new 30,000-psi working pressure rated wireline pressure control equipment (WPCE).
The Aberdeen-headquartered company's engineering department designed and built the equipment, the world's first, within a year. It is in response to increasing challenges for oil and gas companies working with ultra-high pressures.
It is the first time WPCE has been designed to such a high working pressure. Developing this innovative equipment involved the creation of a new design methodology and the use of very high-strength materials such as titanium and Inconel. The equipment was then pressure tested in NOV ASEP Elmar's 60,000-psi rated pressure test bay in Westhill, Aberdeen.
The new equipment was first used by a U.S.-owned oil and gas exploration company on its ultra-deep well in the Gulf of Mexico. The equipment was nicknamed 'NOLA', after New Orleans, which is the hub of oilfield operations within the Gulf of Mexico.
NOLA was chosen for the well due to expected pressures in excess of the capability of current 20,000-psi WPCE. Developing this equipment ensures that NOV ASEP Elmar has the technical expertise to support clients as the search for oil and gas moves into more challenging environments.
ASEP Elmar has always adhered to the principle that fully certified products ensure quality, reliability and safety and in keeping with this the NOLA equipment has been third party witness tested and certified. A third party representative was present for most of the year long build cycle.
Carl Wood NOV ASEP Elmar Engineering Director said: 'The NOLA project has been a challenge for our team in so many ways but has also been an opportunity to demonstrate what the most highly qualified and motivated design engineers can achieve when equipped with the latest modeling and design software. We worked closely with our client through the process and we were grateful for their input. The success of this first project is testament to NOV ASEP Elmar's commitment to developing the innovative technology which is required by the oil and gas market."
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Books/Chapters Most Popular
Creating a Community of Purpose: Whole Foods Market: Management Innovation in Action
Gary Hamel; Bill Breen
Price: $6.93
This chapter provides a portrait of Whole Foods Market and its game-changing business model, in which a company is not just a company but a community of people working to make a difference in the world, and mission matters as much as the bottom line. This chapter was originally published as chapter 4 of "The Future of Management."
Learning objective:
To examine the uniquely effective and innovative management model of Whole Foods Market.
Subjects Covered:
Business models; Employees; Innovation; Management philosophy; Organizational structure; Social enterprise; Values; Visionary management
- Industry: Grocery stores
- Publication Date:
- Oct 9, 2007
- Discipline:
- General Management
- Source:
- Harvard Business Press Chapters
- Product #:
- 18p, English PDF
- Also Available in:


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Used cars for sale in in Dartmouth
103 results found for your search
Used cars for sale in in Dartmouth
Used cars for sale near in Dartmouth. Auto123.com's car classifieds offer an impressive selection of second hand vehicles available in in Dartmouth, including many used cars, trucks and SUVs. With the help of the various options in our search engine, you can easily browse through our inventory and find the exact used vehicle for sale in in Dartmouth that you are looking for.


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The Newlywed To-Do List
So you just got married, what's next? Luckily we have discovered a great check list for all you newlyweds to follow along with.
So you just got married, what's next? Luckily we have discovered a great check list for all you newlyweds to follow along with.
I recently saw a Facebook post from my cousin acknowledging the 100th wedding anniversary of my grandparents.
Talk about wedding crashers! This couple got married in a very cool ceremony aboard a hot air balloon, but the end of the nuptials didn't go quite as expected.
The father-daughter dance is one of the most memorable parts to any wedding. The father's last dance with his baby girl before giving her away. So what happens if you're father has passed away? One bride got a big surprise from her brother, and a few other family members at her wedding. WARNING: TEAR JERKER ALERT.
So, everyone has eaten, all the special dances are done, and its time to PARTY!! What songs do I play to really get people pumped up to dance at weddings?
I recently DJ'd a wedding reception at Rachel's Lakesider. This place is a perfect place for one of the most popular items to enhance the look and feel of a reception room.
When you think about them, there are many not just good, but great wedding movies.
Fun 107's Bridal Show is coming up! Make sure you keep these top 50 Wedding do's and don'ts in mind as you plan your special day! I can tell you, personally, It will make things easier and less stressful in the long run.
With our Fun 107 Bridal Show coming up, it got me thinking about all the weddings I was a part of this past season, and how many brides decided to do the whole garter and bouquet custom.
Every bride is looking for that perfect look to go along with that beautiful dress. An updo can be simple and elegant, and here is a great way to do it.


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Curtain Color
Ruby05August 5, 2014
I recently painted my living room Pumpkin Butter by Behr. Im looking for curtains that would make the room pop.
I would say it would depend on what else is in your room. What colors is your trim, etc? I would probably use a color that would not overpower the beautiful pumpkin butter and something that might sit easily with other elements, like a natural hemp color.
Thanks for all the responses They were very helpful. The couch is a wine color, the trim is white, and tables are dark mahogany.


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ALBUQUERQUE, NM, United States | Member Since 2014
"Minus one star for preachiness"
Great story idea and fairly well executed. I deducted a star for preachiness. Some of it is essential to the story, but IMHO it's overdone a bit. Michael Page's performance was good, but didn't grasp my attention in any special way. If you like classic SF and Horror, but missed Wilde's contribution to the genre along the way, then it will be worth your time, but probably not a credit. I bought it for $0.99 by getting the Kindle version (free) first under Amazon's offerings of classics at low prices to introduce WhisperSync. At $0.99 for e-book and a-book, you can't go wrong. If you haven't discovered this secret, and read Kindle e-books, check out classics on the Amazon site. You'll find that many are very inexpensive or free and entitle you to the a-book for $0.99. It's a great way to add classics to your library
"Very entertaining, highly recommended"
This work contains a lot of profanity that I don't believe is appropriate to the situations; however, it is very exciting and often humorous. Don't assume that I was offended, not even close, but I prefer realism. I don't think a stranded astronaut would leave audio logs, as in the story, in anything but mostly professional language.
That said, I enjoyed 'The Martian' greatly. The author obviously did a lot of research into the technology behind space travel, and the effort added a lot of value to the novel. The audio quality and the performance were excellent.
Just short of a must for sci-fi fans.
"Just couldn't get into it"
It's great of Audible to provide such an outstanding performance for free. However I just couldn't get into the stories. In fact, the first story sounded like it was written for small children.
This is still a great story. It doesn't feel At all dated. Great performance.
"Informative and Entertaining"
I love the Great Courses series. This series of lectures is a worthy contribution. It is always informative, well organized, and sometimes entertaining. I would highly recommend it to anyone interested in an overview of the subject. The only reason that I didn't give it 5-stars, is that there was nothing that jumps out at the listener as really special is terms of content or delivery. After all, it's a lecture series obviously intended to summarize the topic, not break new ground.
"Not quite as good as I expected from Sanderson."
Very xmen-ish and lacking in original core ideas. Humans who have gained super-powers of various kinds after the arrival of "Calamity," which goes unexplained in this first volume. The domination of these gifted people over others. A resistance leader called the "Prof." Some of the the super-powers, and those of one minor character in particular, are just too cartoon-like for my tastes.
All of that being said, the story itself was very entertaining. It has several twists and turns. Sanderson drops enough hints that I had guessed most of them by the end, but I think that was what he intended.
The reading was very good, but several of the character voices sounded too similar to me, hence the five to four reduction for performance.
Overall, I'm looking forward to giving the next installment a go. Don't expect anything as epic, or as deep, as Sanderson's contributions to 'The Wheel of Time' series. All-in-all, an enjoyable ride and worth the credit.
"The worst of an uninspired series"
I have found the characters in all three volumes of this series to be childish beyond belief. I'm not sure about Bova's background (note to self: have to look that up), but I can't accept that the type of people who would be selected for a series of missions to Mars would behave like 5-year-old children. It's routine, in this series, for team members to flatly refuse the orders of their assigned superiors with no attempt to hide/disguise it. Sorry Ben, but I believe the carrot and the stick wielded by any future interplanetary mission commanders would be too potent for mutiny to be a routine occurrence. Sure, there are behavioral outliers in any system, but not to the extent that Bova would sell to us. The ending of the series, was contrived and uninspired.
Bova tries to explore, throughout the series, the conflicts between science and religion. In fact, it's a major theme. It could have added value to the work, if not done in such an unrealistic, over-the-top way. Bova puts large numbers of significant religious leaders on the intellectual level with those who still say the moon landings were all a hoax. Again, there are always a few nuts in the mix, but they are not dangerous unless violent. It's the sane-sounding extremists in any belief system (secular or religious) who are a threat. Bova totally missed the mark. It will take several tremendously positive reviews before I will be spending my reading $$$ on Bova's work, again.
That said, I always enjoy Stefan Rudnicki's work. He has the kind of voice that adds enjoyment to the experience and a great deal of ability.
"Hillarious and thought-provoking"
It's not very often than I laugh out loud when enjoying a book, but this one did it for me several times. If you are easily offended by language or sexual themes, then this might not be for you. It's what you would expect from a late-night comedian. Ferguson takes aim at several deserving targets, including Hollywood and televangelists. No race, religion, or nationality is safe. While having a good time with us, the author asks serious questions about life and death, religion, sexuality, marital fidelity, and human gullibility.
Unlike some authors that have read their own work, Ferguson does an outstanding job. This is as you would expect, since his is an entertainer. Some books make better audiobooks than others. This work jumps from protagonist to protagonist and location to location without immediately obvious ties. You have to follow closely and remember the characters from earlier scenes. I wouldn't listen to this one when distracted, or you might get lost.
I didn't see the tremendous depth that some reviewers claim to find, but I had a really good time.
"Outstanding presentation of a SciFi classic"
The 'Ender' series has been one of my favorites since it's release. This presentation is first-class.
To me, the quality of a work of fiction is defined in two parts, the basic idea/ideas of the story and the execution. IMHO 'Ender's Game' rates among the best in both areas. The unique storyline constantly revolves around the ethical question of whether the end justifies the means. Given a choice, in our daily lives, to win, or to stand on our principles; which is correct? Is true victory the art of finding a way to do both? Ender and his teachers face these questions daily.
This version is basically true to the intent of the original. Since it is dialog, rather than narration, some changes were necessary to fill-in the missing narrative. I found the net result to be entirely positive. The performances range from pretty good to outstanding.
Overall, this is an excellent way to enjoy the beginning of this epic SciFi series; however, I recommend that those who are new to Ender begin by reading/listening to the original.
"A must read. Close enough to reality to be scary"
This work is a classic for a reason. I, personally, found some of the manipulation of the populace by the elite to be a bit too much for belief. However, after finishing this book, you will begin to see Orwellian ideals manifest themselves in the present world. The near complete control of information by N. Korea, China, and some Arab states comes to mind. You will see examples much closer to home, such as the practice among western politicians of stating something that they know to be wrong with great conviction to convince the public of its truth. The phrase "food for thought" must have been invented with '1984' in mind.
Simon Prebble's performance was outstanding.
"Informative and well organized"
This is my second series of lectures by Professor Mark W. Muesse. Both have been a pleasure to hear. I would classify this series as freshman- or introductory-level. It probably would not benefit any but the most casual religious scholar.
I feel that I came away with a good basic understanding of the historical facts, as they can be determined, and the teachings of these four individuals. Great care was taken to provide historical and cultural context for each. The work avoids any judgement about the validity of any religious doctrine.
When we experience deeds performed in the name of a doctrine, the obvious question is whether or not the actions reflect a rational interpretation of the originator's intention or are simply extremist excuses for the actions. An impartial scholar would be the ideal individual to examine this question; however, Professor Muesse makes no attempts in this area. Perhaps this issue was just not the focus of the series, but since the atrocities committed in the name of various religions are a part of their history, he loses one star for political correctness.
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McCrae, Jeremy and Judd Show Off Big Brother Tattoos [PHOTOS]By: Annaka Turner on October 16, 2013
Big Brother 15 cast members McCrae Olson, Judd Daughtery and Jeremy McGuire hit up a tattoo parlor in Tennessee earlier this week to commemorate their time on the show. The three BB15 guys were inked with three versions of the infamous Big Brother veto. McCrae's girlfriend and showmance partner Amanda Zuckerman documented the fun on her Instagram feed.
While McCrae and Judd went for a full veto symbol, Jeremy opted for a tiny
capital V "XV" on his big toes for a more discreet tribute. (Correction on Jeremy's tattoo. Thanks to reader Heather!) McCrae had his veto symbol tattooed on his right shoulder. Judd chose an odd spot on his right side over his ribs, an area easily hidden with his arm down. We just have to ask — why even get a tattoo that you want to be hidden all the time?
McCrae's girlfriend (and rumored fiance) Amanda Zuckerman was reportedly with her boy toy in Tennessee for a promotional event but did not opt to join in on the tattoo experience. Next up, McCrae and Amanda will be headed off to a meet and greet event in Sunrise, Florida at the cost of $25.00 for admission (the ticket also includes a Panthers hockey game).
Would you get a tattoo to commemorate being on the show if you were ever on Big Brother?
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Recent Big Brother 16 News from Big Brother Access:
- Big Brother 2015 Casting Begins In March For Season 17
- Frankie Grande Donates Big Brother 16 Winnings to Charity
- Watch Big Brother On CBS All Access With Free Month Trial
- Big Brother's Donny Thompson Loses His Groundskeeper Job
- Big Brother 2014 Houseguests Reunite for Frankie Grande's 'Rock of Ages' Debut [PHOTOS]


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Devin StarlanylI have seen the magic of guaifenesin and the program in What Your Doctor May Not Tell You about Fybromyalgia work.
— (Devin Starlanyl, author of The Fybromyalgia Advocate)
Patients suffering from fibromyalgia experience a variety of painful and debilitating symptoms, including chronic fatigue, joint and muscle pain, chronic bladder and vaginal infections, depression, insomnia, and disorientation.
Recognized as a disease by the World Health Organization in 1993, ...
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Patients suffering from fibromyalgia experience a variety of painful and debilitating symptoms, including chronic fatigue, joint and muscle pain, chronic bladder and vaginal infections, depression, insomnia, and disorientation.
Recognized as a disease by the World Health Organization in 1993, fibromyalgia has been treated in the past with medications to relieve symptoms, including antidepressants, analgesics, and narcotics. These remedies have not worked for everyone.
Guaifenesin is an inexpensive medication used in over-the-counter products for nasal congestion. But in his studies, Dr. St. Amand discovered that this drug, taken in the proper dosage, is the first effective treatment for reversing fibromyalgiawith no known side effects.
Dr. St. Amand is the country's foremost expert on this subject and is himself a past sufferer of the disease. Drawing on Dr. St. Amand's firsthand experience and filled with the latest research on the subject, this book also offers complete appendices that include Internet user groups and dozens of support organizations for people with fibromyalgia and for those using guaifenesin.
In this groundbreaking book, Dr. St. Amand, an experienced endocrinologist and UCLA assistant clinical professor, presents his amazing discovery, the result of forty years of research based on his own experience with fibromyalgia and that of hundreds of his patients. This book offers the first effective protocol for reversing this disease: a program that uses guaifenesin, an inexpensive, safe medication available from your doctor. The authors have seen symptoms eliminated and normal living restored in an astonishing 90 percent of the fibromyalgia sufferers they properly treated with guaifenesin. Now you too can discover:
About the Authors:
R. Paul St. Amand, M.D., is a graduate of Tufts University School of Medicine. He has been on the teaching staff at the Los Angeles Harbor/UCLA Hospital, Department of Endocrinology for over forty-three years. He is currently an assistant clinical professor at the UCLA School of Medicine. Dr. St. Amand discovered guaifenesin's use as a treatment for fibromyalgia, and his work is cited wherever the substance is mentioned.
Claudia Craig Marek, M.A., is a medical assistant tutored, trained, and taught on the job by Dr. St. Amand. She has co-written medical papers with Dr. St. Amand and has counseled fibromyalgia patients on the use of guaifenesin for the past seven years.
Having fibromyalgia means many things change, and a lot of them are invisible. Unlike having cancer or being hurt in an accident, most people do not understand even a little about (this illness) and its effects, and of those that think they know, many are actually misinformed. -J. M., Texas
It can start off quite subtly: a bit of muscle pain, along with some generalized aches and stiffness. Then there are periods when concentration is impossible, a day or two of overwhelming fatigue, and maybe a little dizziness, cramps, and diarrhea. Symptoms come and go at first, and it's easy to chalk them up to a mild case of flu that never quite localizes, to overexertion and too much stress in your life.
Then, one day, you realize it hasn't gone away-it never goes away anymore. One part or another of your body always hurts. You feel stressed and irritable all of the time. You wake up tired every morning. In short, you haven't felt "right" in a long time. The symptoms begin to worsen, and you notice new ones. Perhaps depression, numbness and tingling of the hands, leg cramps, stiffness, headaches, or bladder infections. Often you can no longer sleep through the night. Sometimes it's pain that keeps you awake; sometimes you don't know what it is that keeps you from falling asleep. When you do sleep, you wake up tired and unrefreshed. You crave sugar or other carbohydrates, and if you give in to this craving, you tend to gain weight and feel even worse. Then, before you know it, bad days outweigh the good ones, and eventually there are no good days, just ones that range from bad to worse.
It feels like coming down with the flu, yet it never manifests fully. It's like being fluish, achy and tired, and embarrassed and discouraged about it because you don't know why or what you can do to make it better or what you did to make it worse. Everyone gives advice but they don't have a clue as to what it's really like. Having people tell you to eat differently and exercise more and not focus on your health makes you just want to isolate yourself because you've already experimented with every possible food plan, supplement, and idea. -Miki K., Hawaii
You become increasingly immobile. Gradually and without realizing it at first, you stop making plans because you never know how you will feel, and you become mostly housebound or bedridden. The simple task of going to the supermarket can be an impossible chore. By now you have visited doctors of various specialties in the hope that one of them will be able to tell you what's wrong and set things right. When the pain is bad, you seek out chiropractors and massage therapists, and maybe you try acupuncture and alternative treatments like herbs or homeopathy. You have had many diagnostic tests run, costing hundreds, perhaps even thousands of dollars. Your friends have offered you a lot of advice about vitamins and nutritional supplements that have helped them or someone they know. But you are already taking a regimen of vitamins, minerals, and enzymes, and you do not feel much better. You may have heard the word "fibromyalgia," and maybe you know whether or not you have it. No one has told you how to treat your disease, although they have many ideas about how to ease your symptoms.
Your life has entered a downward spiral of pain, depression, and fatigue. You have a great deal of guilt about not being the person you used to be. Unless you are blessed with an exceptional companion, your personal relationships have suffered or completely fallen apart. You worry about your ability to care for your children. You may even contemplate suicide.
It feels like everyone around me is normal and happy and having a good time and I'm so different. I want to have a few normal days. I don't fit in anywhere because no one understands. People laugh and say "You look fine" but I'm dying inside and I can't explain it to them. I'm so tired of pretending I'm okay when I want to scream. I have kept a positive attitude for so long but it's exhausting and I just can't do it anymore. I wish I could just go away somewhere and hide. -Susie
This is an oversimplified picture of what it's like to have fibromyalgia. Those of you who have it know that it is far more involved than this. I know what you're going through. I am intimately familiar with the personal struggles that each and every one of you has experienced with this illness either as sufferers or as their supporters. I have lived with your pain, your fatigue, and your despair.
I have spent my entire medical career treating patients with symptoms such as these and more. Headaches, jaw and facial pain, abdominal discomfort, dizziness, memory lapses, vulvar and bladder pain, itching and rashes, all plague fibromyalgics. Until recently, doctors told patients like you that your illness was due to "nerves." And, to underscore this diagnosis, patients were reminded that the pages and pages of tests run on them had shown "nothing wrong."
Fibromyalgia is prevalent in all ethnic groups in all parts of the world. In North America, it is estimated that about five percent of the adult population suffers from this disease, although I believe the actual rate is higher. Conservatively then, some twenty million Americans suffer from fibromyalgia and its related disorders-most are women, with the ratio of women to men at about five to one. There is some evidence, mostly anecdotal, that this statistic may be skewed due to the fact that men are often either misdiagnosed or less likely to visit a doctor. Rheumatologists say fibromyalgia is the most common disorder they see.
Another twenty-five million people suffer from chronic fatigue syndrome, which I (and most other physicians) believe is the same disease. I have good reasons to conclude through my work that today's fibromyalgia is the prelude to tomorrow's osteoarthritis that afflicts another thirty-five million people. Adding these numbers would suggest that one third of our population will suffer with some of the symptoms of fibromyalgia at some point in their lives. And this does not include those who have been diagnosed with other "syndromes," such as myofascial pain, chronic candidiasis, vulvar pain, irritable bowel and irritable bladder, and so on-who in all probability have fibromyalgia as well.
My rheumatologist told me I was too old to have FMS. At that time I was fifty-four, never mind the fact I had had symptoms most of my life. The disease had become "full blown" when I was about fifty-one.... After another year of suffering, I diagnosed myself via the Net. My DO (Doctor of Osteopathy) sent me back to the same rheumatologist because he is the only board-certified one in our area. At that time he told me I was too old to have FMS but even if I did there was nothing that could be done.... I have since been diagnosed with FMS by three other doctors, all of whom have told me the only thing they could do was treat my symptoms. I was as good as I would ever be and would get much worse. -Betty, Texas
"Rheumatism with painful hard places" which can be felt in various locations on the body is considered the first description of fibromyalgia in modern medical texts, by a doctor named Froriep in 1843. Sir William Gowers of University College Hospital in London, who began by studying his own lumbago, initially dubbed this disease "fibrositis" in 1904. Dr. Gowers observed that his patients were also exhausted and that the disease was "so painful it would make a strong man cry out." He tried everything he could think of in an attempt to relieve this pain, including injecting cocaine into the tender points (it didn't work very well) and having patients take a newly discovered drug called aspirin that, he observed, didn't work very well either. "Fibromyalgia," a Greek word meaning pain in the muscles, has now all but erased fibrositis and rheumatism as the name of this disease.
On New Year's Day 1993, fibromyalgia was officially declared a syndrome by the World Health Organization (WHO) in the Copenhagen Declaration. It was declared the most common cause of widespread chronic muscle pain. As a new entry in the ICD code (International Statistical Classification of Diseases and Related Health Problems) it became an official diagnosis that, among other things, a doctor could use to bill insurance companies and to label a patient disabled. The WHO decided to incorporate into the definition of the disease the American College of Rheumatology's 1990 definition penned by Drs. Muhammed Yunus, Hugh Smythe, and Frederick Wolfe. This had carefully detailed the location of eighteen tender points symmetrically located around the human body. The presence of at least eleven out of eighteen of these was considered the gold standard for diagnosis, along with muscle pain.
But the World Health Organization went a little farther. The Copenhagen Declaration added: "Fibromyalgia is part of a wider syndrome encompassing headaches, irritable bladder, dysmenorrhea, cold sensitivity, Reynaud's phenomenon, restless legs, atypical patterns of numbness and tingling, exercise intolerance, and complaints of weakness." It also recognized that patients are often depressed.
Today, thousands of medical articles later, fibromyalgia is almost universally recognized as a distinct illness. Sadly, there remain a few doctors who still try to tell patients it is simply a catchall name for a collection of symptoms shared by a group of neurotic women, but luckily they are increasingly rare. Despite so many articles and so much speculation, much of fibromyalgia remains poorly understood. It is a complex and chronic disease that causes widespread pain and profound fatigue-accompanied by a range of symptoms that make simple, everyday tasks daunting, difficult, and sometimes even impossible.
Once upon a time, a lifetime ago, I was a gymnast, played in tennis leagues, golfed, played on a softball team, and panned for gold in the Colorado mountains.... Now I am lucky if I can walk to my mailbox-usually I have to drive. If I can make the stairs, I go down to check on the laundry situation, or go upstairs to see if the dust has carried away the entire floor. -Gloria
Symptoms affect widely disparate parts of the body. Doctors don't always realize that tenderness in the neck area, frequent bladder infections, and brittle nails, for example, are symptoms of the same illness. Patients, often young women, look "well" and many have learned to put up a facade in the workplace or with friends. A growing number of people have now heard of fibromyalgia and know someone who has it. Lists are available that detail the multiple symptoms of the disease, but it remains a phantom illness that has few concrete findings to the casual examiner. It still lacks a laboratory test to confirm its existence, and no scans or X rays can detect it. For these reasons, fibromyalgia is often described as an "invisible disability."
Yet a well-conducted history will unveil the chronology of the cyclic symptoms that point to a diagnosis. This is easily confirmed by the many abnormalities in muscles, tendons, and ligaments revealed by a detailed examination. Some doctors enjoy semantics and argue whether this is a syndrome or a true disease. "Disease" is exactly that: lack of ease, and fibromyalgics are certainly qualified to wear that name. Symptoms and findings that regularly appear together in a number of patients are grouped as a "syndrome." Congratulations! Fibromyalgia is that, too.
The painful areas of tenderness are often superimposed at the sites of previous injuries or surgery, so some believe that it is caused by trauma. We believe that there are good scientific reasons why this should be, but we also believe the disease-syndrome is inherited. Since eighty-five percent of fibromyalgia patients are women, at least one gene is undoubtedly on the X chromosome. But there must be more than one gene involved, since we have seen the illness begin as early as the age of four and as late as the age of seventy-four. That spread would be impossible to explain with only one defective gene. There is no doubt in my mind that there is a genetic predisposition to FMS. My eighty-six-year-old father has had it since my teen years. My mother recently told me when I asked about his leg pain that the doctor said years ago that there were lumps in his legs. -M. Bush, Alabama
Although fibromyalgia is not a terminal illness, it is a demoralizing and debilitating one. The symptoms can be unbearable-so unbearable that the so-called "Suicide Doctor," Dr. Kevorkian, has helped several fibromyalgia patients end their suffering. In 1997, one of these fibromyalgics was forty-year-old Janis Murphy. After her death, her father spoke out about his daughter's condition. "Over the years, I've seen my daughter experience intractable and unrelenting pain." He hated losing his only child, but "there are things in this world worse than death."
The currently accepted method for helping fibromyalgics is to recommend exercise (knowing the patient can't do it) and to employ a war chest full of chemical Band-Aids used simply to palliate the lengthening litany of symptoms. Medical professionals unwittingly promote increasing disability when they prescribe ever-stronger medications that, sooner or later, deplete energy even further and deepen the mental haze. Along with the failure of exercise programs, massage, and physiotherapy, patients accept their lot and become victims of their disease.
To make bad matters even worse, long-term disability insurance companies have now entered the fibromyalgia fray and help to confound progress. It is to their advantage to insist that the disease and all of its variations stem from psychiatric disorders. They often have no difficulty in finding a psychiatrist who will agree. Since the vast majority of insurance policies do not cover mental disability beyond a specified time, there is a great deal of money at stake. Fibromyalgia cases have reached near epidemic proportions in the form of U.S. Social Security disability claims, workers' compensations, and accident litigation. As many as twenty-five percent of American fibromyalgia patients have received some form of disability or injury compensation. We are first to agree that the country can ill afford to swell these ranks. But we cannot turn our back on very real suffering, either.
Although there is no consensus as to the source of the disease, I postulate throughout this book, hopefully in simple enough terms, that it is caused by an abnormality in phosphate excretion. As I have already suggested, this inherited problem appears to me to be due to a genetic defect.
Excerpted from What Your Doctor May Not Tell You About Fibromyalgia by R. Paul St. Amand Claudia Craig Marek Copyright © 1999 by R. Paul St. Armand, M.D. and Claudia Craig Marek . Excerpted by permission.
All rights reserved. No part of this excerpt may be reproduced or reprinted without permission in writing from the publisher.
Excerpts are provided by Dial-A-Book Inc. solely for the personal use of visitors to this web site.
|Part I
|The Plan for Conquering Fibromyalgia
|Chapter 1
|An Invitation to Join Us and Find Your Way Back to Health
|Chapter 2
|The Fibromyalgia Syndrome: An Overview of Symptoms and Causes
|Chapter 3
|Guaifenesin: How and Why It Works
|Chapter 4
|Know Thine Enemy: Salicylates
|Chapter 5
|Hypoglycemia, Fibroglycemia, and Carbohydrate Intolerance
|Chapter 6
|The Protocol
|Part II
|Understanding the Many Facets of Fibromyalgia
|Chapter 7
|Genitourinary Syndromes
|Chapter 8
|The Irritable Bowel Syndrome: Fibrogut
|Chapter 9
|The Brain Symptoms: Chronic Fatigue, Fibrofog, Fibrofrustration
|Chapter 10
|Other Symptoms
|Chapter 11
|Pediatric Fibromyalgia
|Part III
|Strategies for the Road Back
|Chapter 12
|Medical Band-Aids: Currently Accepted Treatments for Fibromyalgia--What You Don't Know Can Hurt You
|Chapter 13
|Coping with Fibromyalgia: What Will Help While Guaifenesin Heals Your Body?
|The Authors' Last Word
|One Thousand of the Most Common Natural Salicylates to Avoid
|Technical Appendix
Posted June 3, 2008
I am a nurse and have suffered from fibromyalgia syndrome for nearly 60 years with many progressing subtle and not so subtle distressing and debilitating symptoms. After reading Dr St Amand's book, I gave it a try with all I had, fibrofog and all. With great care to eliminating salicylates, bioflavonoids, etc... as prescribed in the book, and starting on the 'protocol', I find myself cycling and improving with each passing month. I feel that for me, this is the most helpful, critical regimen and protocol to recover from fibromyalgia. It is IMPERATIVE to be COMPLIANT as to avoiding the offending culprits, otherwise the protocol 'and over the counter medication' won't work at all. The website offered in the book is a great help with the regimen. This book and the author's website in the book, are a must.
2 out of 2 people found this review helpful.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted March 20, 2010
I found this book to be just what I was looking for to make me more aware of the condition I was being tested for. Very easy to read and good information. It made me feel much more comfortable being able to pin symptoms down that I was having.
1 out of 1 people found this review helpful.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted December 4, 2007
I came across this book in the library and decided to take a look at it. I thought it was probably another scam, but once I started the book I found it extremely interesting. I must have finished it in 3 or 4 days. It explains so much about the various symptoms of fibromyalgia and offers hope for a legitimate, if unproven treatment. Through joining the online protocol support group, I have found numerous people who have had success on this protocol. I hightly recommend this for sufferers or family members of people who have fibro.
1 out of 1 people found this review helpful.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted April 15, 2009
Thought the book was full of useful information. Also to the point.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted December 27, 2008
I've been on the protocol for a year and a half. I just had a check up with Dr. St. Amand last week and I've improved so much on the protocol that he said if I were to just walk in off the street and ask to be evaluated he would not be able to give me a definitive diagnosis of fibromyalgia. When I first started with him I had 63 trigger points and I'm down to 27! While I still experience the cycling/symptoms they are much better than before. My children have it also and are on the protocol and they are improving. Some people think this is nonsense but there is no doubt in my mind it's working because I'm seeing and feeling the results. Those that aren't willing to try this don't realize the quality of life they are missing out on.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted May 19, 2008
Having suffered many years with this illness, I was looking for something that made sense and explained why my muscles hurt so much. Now I know! It was a good read with explanations a lay person could understand. I started the treatment plan and have seen some slow but real improvements. I would recommend it to any sufferer. The authors also have an online support group to answer the many questions that pop up.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted October 2, 2002
Worth a look for any person that is struggling with this terrible condition. If you have back pain too, I can recommend "The Multifidus Back Pain Solution." It's based on research and treatment consist of a simple exercise you do at home for your multifidus muscle.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted November 13, 2000
I saw 22 doctors and an entire team at Mayo Clinic. No one could help me. They said my problems were due to 'being a woman, having 4 children, or menopause'. When finally diagnosed with fibromyalgia, they still couldn't help me, I should just learn to live with the pain. I KNEW there had to be something that I could do to get well. The answer is here, in this book by Dr. Paul St. Amand. I am now on guaifenesin (it's not herbal, it's an ingredient found in Robitussen, and is safe & approved by the FDA). I knew I was getting well when my 8 year old said 'mom, this is how you used to be'! It works, try it.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted September 13, 2000
This is the miracle book of all books. This book is well written, easy to understand and the answer to Fibromylgia recovery by utilizing Guaifenesin. You will see that you are not crazy, you are not a hypochondriac and that you do have a legitimate illness despite all tests that were negative. You will feel vindicated after all your many trips to many doctors who could not tell you why you ached, felt tired, were dizzy, had headaches, IBS symptoms, cognative problems and a myriad of symptoms that you have had over many months or years or a lifetime. I have been on Guaifenesin for 26 months and am enjoying a wonderful life on my journey to recovery. A miracle indeed considering I was bedridden for most of 1998 before Guaifenesin. I have had Fibromylgia all my life.
0 out of 1 people found this review helpful.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted May 14, 2000
If you have FM, you have to read this book. I bought this book, read it and within a couple of weeks I was sitting in Dr. St. Amand's office. I've been following the protocol he outlines in this book for 2 months now and already do MORE than I could do a year ago. Thank you Dr. St. Amand, Nurse Claudia & my fellow guai'ers for giving me my hope, health and life back!!!Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted May 11, 2000
This book is an absolute must for anyone with fibromyalgia. It includes a detailed accounting of how you can actually reverse the disease, not cover it up with drugs or other treatments. The medication has no side effects and is very inexpensive. Included in the book is detailed information on diet recommendations, products to avoid and internet links to a support group which is very active and supportive to anyone wishing to find out more information on this protocol. The authors regularly read the email and answer pertinent questions. You can't get any better help than from the book and the mailing list support group.
0 out of 2 people found this review helpful.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted May 10, 2000
Most of the books I have read offer advice on how to manage the symptoms of FMS, but no real insight into the cause or possible treatment. This book is a real breath of fresh air. The description of the symptoms and cause are clear and easily understood, the guaifenisen treatment protocol is explicit enough that the committed individual can get help with minimal reliance on their care provider. I used this book to help obtain a guai rx from my doctor and followed Dr. St. Amand's protocol. Nine months later, I can honestly say I have my life back. My doctor is so impressed with my progress that he is now recommending the book to his other FMS patients! Thank you, Dr. St. Amand and Claudia!Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted May 11, 2000
I bought this book on a Saturday night and I was seeing a Dr. and getting the recommended treatment by the following Saturday. It is a great book with a great premise. The protocol involves a very simple medication called guaifenesin and there is a support group on the internet who will help you every step of the way. If you are like others with fibromyalgia you are discouraged, sick, and at the end of your rope. This book will give you hope. I promise.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted January 24, 2000
This is very informative book for anyone that has been diagnosed or suspects the diagnosis of fibromyalgia. I gained a lot of knowledge even though I have been using the subscribed treatment protocol for many years. THIS PROTOCOL WORKS! Please check out this information and don't let anyone tell you that you have to suffer with bandaid cures if you have this disease.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted October 2, 2010
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Posted June 7, 2010
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Posted March 25, 2009
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Posted January 28, 2010
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Posted July 2, 2010
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text:
It is one of the most honest examinations in the country: former Union Home Secretary
Improving knowledge base on a continuous basis and developing reading and writing habits were key factors in the preparation for Civil Services examination. It is not just the knowledge that matters, but using the knowledge smartly was the secret towards cracking civil services.
These seemingly simple, but highly effective, tips were shared by top bureaucrats with a huge gathering of Civil Services aspirants at a session on "Civil Services – A Choice for Youth", organised by The Hindu Education Plus in association with Sri Chaitanya IAS Academy here on Sunday. The session was attended by over 1,000 people.
Former Union Home Secretary and Padmabushan awardee K. Padmanabaiah advised the students to start reading and writing about issues as the former would enhance knowledge while the latter would help in effectively putting those points on the paper in the examination.
Start reading a newspaper which would help in acquiring knowledge on different issues and read different books which would add value to the knowledge acquired, he said. Removing the false notions that candidates with humanities background do well in Civil Services, he said that 221 candidates from medical-related streams were chosen last year and a very high number of successful candidates from the State came from the Acharya N.G. Ranga Agricultural University and NTR University of Health Sciences.
With regard to choosing the optional subjects, he said that candidates should choose subjects that they have passion for than preferring perceived high scoring subjects. He ruled out political influence in selection of candidates and said that it was the most honest examination conducted in the country.
The Commissioner of Panchayat Raj and Rural Development Poonam Malakondaiah said that IAS attracts the best brains in the country and its profile was unmatched. It is a challenging, adventurous and satisfying career even for women as it gives power to serve people.
Professional degrees
She said that strategic planning was a must to crack the test as one would have to compete with the best in the country. She favoured candidates with professional degrees coming into services as the job is multi-faceted now and they can use that expertise to serve the country and people. She recalled how her knowledge in Biotechnology helped to tackle the Monsanto issue effectively.
She said that parents had a huge role to play in the success of the aspirants. Right atmosphere, proper encouragement and nutritious food at home would help the aspirants prepare well. She disagreed with the views that honest people can't work now and said that no service can force one to be corrupt.
Revenue service
Explaining the importance of Indian Revenue Service (IRS), Parneet Singh Sachdeva, Commissioner of Income Tax, said that it provides a lot of independence at work.
It is a cutting-edge service and provides selected candidates with unmatched leadership qualities.
It was a high-profile job as the highly efficient IRS officers deal with the best brains across the world, representing the country on various assignments.
On the exam, he said that hard work, dedication and devotion were the secrets to success.
Later, answering the questions, the panellists said that choosing optional subjects was a personal choice. "Start reading newspaper editorials and articles on various issues and the knowledge acquired will be useful not just in the examination but throughout the service," was their advice.
Y. Mohan Rao, Principal, Sri Chaitanya IAS Academy, explained the preparatory courses being offered by them for Intermediate and Degree students apart from Graduates.


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I am a young professional audio and sound engineer. I have been doing this since 2001 and can't imagine doing anything else with myself. I love to travel and go to concerts.
I respect other peoples things as if they are my own and tend to be a bit anal when it comes to order in the house. Usually when staying with friends, their place is cleaner when i leave then when I arrived.
In life i believe that everything in the universe is exactly as it should be when it should be, good or bad...
If you wanna learn to fly, you can't hang out with chickens!
And shoot for the moon, even if you don't make it you"ll still be amongst stars.


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Looks good mate! Will this work for the Vodafone N7105T?
Hey mate have you tried the rom on your vodafone N7105T model? If so, were you successful in the process? Cheers
XDA Developers was founded by developers, for developers. It is now a valuable resource for people who want to make the most of their mobile devices, from customizing the look and feel to adding new functionality.
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Peacock Alley Alyssa Sham
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Peacock Alley Alyssa Sham
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|Product Type: Sham
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|Primary Material: 100% Cotton
|Additional Materials: Feather and down form
|Number of Items Included: 1
|Cleaning Method: Machine wash
|Gender: Unisex
|Life Stage: Adult
|Product Care: Machine wash cold with a mild detergent All natural fibers will shrink to some extent Please refrain from using bleach or other harmful chemicals and detergents on fine linens
|Country of Manufacture: Portugal
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Peacock Alley Alyssa Sham
About the ManufacturerA Peacock Alley customer is a customer for life. Peacock Alley is committed to producing luxurious quality bed linens and other products to a wide range of customers, encompassing specialty retailers, high-end department stores, high-end mail order catalogs, company-owned stores and through the Peacock Alley website.Duvet covers, coverlets, shams, sheets, bed skirts, bath robes and shower curtains are just a few among a wide range of products manufactured and imported by Peacock Alley.
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Happy Thanksgiving
I'm cooking away tonight and will be busy tomorrow so I wanted to wish all of you and your pets a fun holiday. Some of you will be gardening, I'm sure.
Honor, Scentimental and PJPII are looking more Christmas than Thanksgiving but I don't have any fall leaves yet so I'll use what I have. At least they smell great.
Yes, Happy Thanksgiving to you, Kitty, and everyone else on the forum. Your bouquet is so fresh and luscious I can almost smell it. And it does, indeed, look like a lovely Christmas bouquet--I'm thinking of peppermint--yum. Diane
Beautiful bouquet Kitty! Yes HAPPY THANKSGIVING everybody!!
I'm cooking the meal at my 95yr old mom's house tomorrow. But tonite I'm staying up waiting for two cheesecakes to get done so I can get them refrigerated before tomorrow. One's vanilla and the other one is blackberry almond. Yum yum! Just wish they'd get done so I can go to bed!
Here's a couple appropriate roses with similar names that look very much alike, but are not the same.
Happy Thanksgiving to you too!
Kitty, I love that bouquet!
Beth, how fun to have Thanksgiving Roses! And a 95 year old Mom. (No big dinner for me to cook tomorrow but still find myself up past bedtime waiting on cinnamon rolls in the oven)
Happy Thanks Giving to you too Nana
Happy Thanksgiving to you also.
This is the first time in many years that I am not cooking a turkey. I am going to be treated to a T-day meal at the Claremont Hotel. The hotel is a grand old hotel and is high in the Berkeley hills overlooking the San Francisco Bay.
Happy, happy to all


text:
Page 1
Concise Two-Step Solution Phase Syntheses of four novel
Dihydroquinazoline scaffolds
Justin Dietrich1,2,4, Christine KaiserØ, Nathalie Meurice4,Ø, and Christopher Hulme1,2,3,4,*
1College of Pharmacy, Department of Pharm/Tox, Divisions of Medicinal Chemistry & Organic
Chemistry, University of Arizona, Tucson, AZ 85721
2BIO5 Institute, University of Arizona, Tucson, AZ 85721
3Department of Chemistry, University of Arizona, Tucson, AZ 85721
4Southwest Comprehensive Center for Drug Discovery and Development
ØThe Translational Genomics Research Institute (TGen), N 5th Street, Phoenix, AZ 85004
Novel two-step solution phase protocols for the synthesis of dihydroquinazolines and fused
dihydroquinazoline-benzodiazepine tetracycles are reported. The methodology employs the Ugi
reaction to assemble desired diversity and acid treatment enables ring closing transformations. The
protocols are further facilitated by the use of microwave irradiation and n-butyl isocyanide to
control the rate of each ring forming transformation.
The elucidation of the complete human genome in 20011 has resulted in a dramatic increase
in the demand for the identification of small molecules to validate the pharmacological
potential of new macromolecular targets2,3. In particular, isonitrile based methodologies4-6,
followed by a variety of secondary ring forming transformations, have shown great utility in
concisely producing highly functionalized and drug-like scaffolds with high iterative
efficiency potential7-9. Methodologies developed in this laboratory have proven quite
productive, delivering examples where initial hits have progressed into clinical trials for the
treatment of both HIV infection10,11 and pre-term labor,12-15 importantly without the need
to 'scaffold hop'. Recently, we have reported a contrite two-step synthesis of
triazabenzulenones16 that represents the first post-condensation Ugi modification
employing two internal amino nucleophiles and a subsequent report that utilized microwave
irradiation with n-butyl isonitrile in place of a traditional 'designer convertible isonitrile'17
to form benzodiazepines and diketopiperazines. Herein, we report two-step syntheses that
yield dihydroquinazolines 1 and 2, and fused dihydroquinazoline-benzodiazepine tetracycles
3 and 4. The tetra-cyclic scaffolds represent a second example of a post-condensation Ugi
modification employing two internal amino nucleophiles and all 4 syntheses rely on the
reduced reactivity of an n-butyl amide carbonyl derived from n-butyl isonitrile relative to
traditional convertible isonitriles to ensure the correct sequence of ring forming events. It
was envisioned that the dihydroquinazoline core could be produced in two steps: an Ugi
*Corresponding Author: firstname.lastname@example.com .
Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our
customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of
the resulting proof before it is published in its final citable form. Please note that during the production process errors may be
discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
NIH Public Access
Author Manuscript
Tetrahedron Lett. Author manuscript; available in PMC 2011 July 28.
Published in final edited form as:
Tetrahedron Lett. 2010 July 28; 51(30): 3951–3955. doi:10.1016/j.tetlet.2010.05.108.
NIH-PA Author Manuscript
NIH-PA Author Manuscript
NIH-PA Author Manuscript
Page 2
reaction with mono-Boc protected 2-aminobenzylamines 5, supporting aldehydes 8, non-
convertible isonitriles 7, and carboxylic acids 6 to yield the condensation product 9 followed
by acid promoted deprotection and cyclization. Both the 1,4-dihydroquinazoline (Scheme
1a, 10) and 3,4-dihydroquinazoline (Scheme 1b, 12) scaffolds can be produced from the
corresponding mono-protected 2-aminobenzylamine input 5 or 11. We have previously
demonstrated a similar acid promoted dehydration of an Ugi condensation product to
generate an aromatic benzimidazole core16,18 and this report expands the use of such
methodology to obtain non-aromatic bi-cyclic rings such as the dihydroquinazolines 1 and 2
with significantly different physicochemical properties and spacial positioning of decorating
Optimal yields for the Ugi reaction were found to occur via pre-formation of the Schiff base
in methanol for 30 minutes, followed by addition of the isonitrile and carboxylic acid inputs
with subsequent microwave irradiation at 100°C for 10 minutes (isolated yields 48-85%).
The Ugi product was then treated with 10% TFA/DCE (irradiated at 120°C) to form the
desired quinazoline scaffolds 10 and 12 core in good yield (46-65% ~ isolated overall yield
for two steps). With this protocol in hand, it was hypothesized addition of a second protected
amine, through the use of an N-Boc protected anthranilic acid 13, would enable formation of
novel fused dihydroquinazoline-benzodiazepines (Scheme 2a and 2b, 14 and 15) after
deprotection and two sequential cyclization steps. However, addition of the bulky Boc-
protected amine group resulted in a dramatic decrease in the yield of the Ugi reaction (<5%).
This effect was also observed in the 1,4-quinazoline series with 2-chlorobenzoic acid
(Figure 3, 30). Circumventing this problem, pre-formation of the Schiff base in toluene
under microwave irradiation with removal of water (MgSO4) provided the Schiff base in
quantitative yields. Subsequent reaction in MeOH afforded the desired Ugi product in 44%
yield [Note: observed by-products arose from methanol addition to the Schiff base and the
Passerini reaction]. Interestingly, reactions in trifluoroethanol yielded similar results – a
strategy that is often successful in reducing solvent participation in the Ugi reaction. A
modest improvement in yield was observed by pre-forming the Schiff base in
dichloromethane in the presence of MgSO4 (microwave, 120°C). Following addition of
supporting reagents, the reaction was irradiated at 120°C for 10 minutes with an acceptable
improvement in yield (56%, Scheme 2a). Removal of the 2 Boc groups, cyclo-dehydration
to the dihydroquinazoline core and concomitant cyclization onto the n-butyl amide, afforded
the desired fused 1,4-dihydroquinazoline-benzodiazepines 14 and 15 in acceptable yields
upon simple acid treatment and microwave irradiation. Not surprisingly, the major side
products of the cascade reaction were the benzodiazepine trifluoroacetamide 16 (24% yield),
and the bicyclic trifluoroacetamide 17 (13% yield).
The scope of the methodology was evaluated with a selection of different reagents.
Cyclization reactions of purified Ugi products were run in series on a Biotage Initiator 8
microwave and were purified in a sequential manner on a Biotage Isolera 4 system utilizing
neutralized silica gel columns. The observed high polarity of dihydroquinazolines can be
attributed to their relatively high pKa values (Table 1). Thirteen examples are presented 18
through 30 containing all four dihydroquinazoline cores with isolated overall yields for the
two-step procedure ranging from 21% to 64% Figure 3.
To demonstrate scaffold uniqueness, virtual libraries for 1 through 4 were enumerated
(comprising scaffold 1—168 compounds; 2—168 compounds, 3—144 compounds, 4—48
compounds) and compared with the 375,000 compounds in the NIH molecular libraries
small molecule repository (MLSMR). A total of 1043 nearest neighbors were indentified
and a principle component analysis21 clearly demonstrates the unique diversity space
occupied by expanded libraries of the four scaffolds described herein Figure 4.
Dietrich et al. Page 2
Tetrahedron Lett. Author manuscript; available in PMC 2011 July 28.
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Page 3
In summary, we have reported concise two-step solution phase syntheses that afford bi-
cyclic dihydroquinazolines and fused tetra-cyclic dihydroquinazoline-benzodiazepines,
which are under-represented in the literature and the MLSMR.22 With amenability to high-
throughput solution phase synthesis, it is expected the methodology will be embraced by the
lead generation community.
We would like to thank the Office of the Director, NIH and the National Institute of Mental Health for funding
1. Bienayme H, Hulme C, Oddon G, Schmitt P. Chemistry. 2000; 6:3321–9. [PubMed: 11039522]
2. Borthwick AD, Davies DE, Exall AM, Hatley RJ, Hughes JA, Irving WR, Livermore DG, Sollis SL,
Nerozzi F, Valko KL, Allen MJ, Perren M, Shabbir SS, Woollard PM, Price MA. J Med Chem.
2006; 49:4159–70. [PubMed: 16821776]
3. Borthwick AD, Davies DE, Exall AM, Livermore DG, Sollis SL, Nerozzi F, Allen MJ, Perren M,
Shabbir SS, Woollard PM, Wyatt PG. J Med Chem. 2005; 48:6956–69. [PubMed: 16250654]
4. Domling A. Chemical Reviews. 2005; 106:17–89. [PubMed: 16402771]
5. Grenet O. Pharmacogenomics J. 2001; 1:11–2. [PubMed: 11913719]
6. Habashita H, Kokubo M, Hamano S, Hamanaka N, Toda M, Shibayama S, Tada H, Sagawa K,
Fukushima D, Maeda K, Mitsuya H. J Med Chem. 2006; 49:4140–52. [PubMed: 16821774]
7. Hulme C, Chappeta S, Dietrich J. Tetrahedron Lett. 2009; 50:4054–4057.
8. Hulme C, Chappeta S, Griffith C, Lee Y-S, Dietrich J. Tetrahedron Lett. 2009; 50:1939–1942.
9. Hulme C, Dietrich J. Mol Divers. 2009; 13:195–207. [PubMed: 19205916]
10. Hulme C, Gore V. Curr Med Chem. 2003; 10:51–80. [PubMed: 12570721]
11. Hulme C, Maggiora GM. Curr Opin Chem Biol. 2008; 12:257–9. [PubMed: 18498777]
12. Hulme C, Nixey T. Curr Opin Drug Discov Devel. 2003; 6:921–9.
13. Liddle J, Allen MJ, Borthwick AD, Brooks DP, Davies DE, Edwards RM, Exall AM, Hamlett C,
Irving WR, Mason AM, McCafferty GP, Nerozzi F, Peace S, Philp J, Pollard D, Pullen MA,
Shabbir SS, Sollis SL, Westfall TD, Woollard PM, Wu C, Hickey DM. Bioorg Med Chem Lett.
2008; 18:90–4. [PubMed: 18032036]
14. Nishizawa R, Nishiyama T, Hisaichi K, Matsunaga N, Minamoto C, Habashita H, Takaoka Y,
Toda M, Shibayama S, Tada H, Sagawa K, Fukushima D, Maeda K, Mitsuya H. Bioorg Med
Chem Lett. 2007; 17:727–31. [PubMed: 17118654]
15. Reiss T. Trends in Biotechnology. 2001; 19:496–499. [PubMed: 11711192]
16. Tempest P, Ma V, Thomas S, Hua Z, Kelly MG, Hulme C. Tetrahedron Lett. 2001; 42:4959–4962.
17. Venter JC, et al. Science. 2001; 291:1304–51. [PubMed: 11181995]
18. Wyatt PG, Allen MJ, Borthwick AD, Davies DE, Exall AM, Hatley RJ, Irving WR, Livermore
DG, Miller ND, Nerozzi F, Sollis SL, Szardenings AK. Bioorg Med Chem Lett. 2005; 15:2579–
82. [PubMed: 15863320]
19. General Preparation of dihydroquinazolines, 19: To a solution of butyraldehyde (164 μl, 1.800
mmol) in methanol (3 mL) in a 2.0-5.0 ml microwave vial was added tert-butyl 2-
aminobenzylcarbamate (200 mg, 0.900 mmol). The reaction was stirred at room temperature for
30 minutes followed by the addition of n-butyl isocyanide (95 μl, 0.900 mmol) and benzoic acid
(110 mg, 0.900 mmol). The reaction was then irradiated for 10 minutes at 100°C. The solvent was
evaporated in vacuo, crude material taken up in 3 mL 10% EtOAc/Hexane and loaded onto a 12 g
silica column with purification performed on a Biotage® Isolera 4 (gradient 10%-20% EtOAc/
Hexane) to yield the desired Ugi product (344 mg, 0.738 mmol, 82 % yield). The Ugi product was
then taken up in 5 mL 10% TFA/DCE, transferred to a 2-5 mL microwave vial and irradiated at
120°C for 20 minutes. The reaction was then poured into a separatory funnel that contained 50 mL
saturated sodium carbonate and 50 mL DCM. The organic layer was collected and aqueous layer
further extracted with DCM (50 ml). The combined organics were dried over MgSO4,
Dietrich et al.Page 3
Tetrahedron Lett. Author manuscript; available in PMC 2011 July 28.
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Page 4
concentrated onto neutralized silica, and purified on a Biotage Isolera (25 g neutralized column,
20% EtOAc/1.5% TEA/Hexane) to yield the desire 1,4-dihydroquinazoline product, N-butyl-2-(2-
phenylquinazolin-1(4H)-yl)pentanamide 20 (209 mg, 0.576 mmol, 64 % yield). 1H NMR (300
MHz, CDCl3): 7.50 (dd, 2H, J=1.8 Hz, J=14.7 Hz), 7.31-7.45 (m, 3H), 7.12 (dt, 1H, J=7.5 Hz,
J=0.9 Hz), 7.05 (dt, 1H, J=0.9 Hz, J=7.5 Hz), 6.98 (d, 1H, J=5.4 Hz), 6.78 (d, 1H, J=7.5 Hz). 6.45
(t, 1H, J=5.4 Hz), 4.83 (d, 1H, J=18.6 Hz), 4.74 (d, 1H, J=18.6 Hz), 4.25 (dd, 1H, J=4.2 Hz,
J=10.2 Hz), 3.29 (m, 2H), 1.7-2.2 (m, 2H), 1.45-1.6 (m, 2H), 1.20-1.40 (m, 4H), 0.91 (t, 3H, J=4.5
Hz), 0.79 (t, 3H, J=4.2 Hz). 13C NMR (75 MHz, CDCl3): 171.05, 158.18, 137.03, 136.62, 130.05,
29.89, 20.52, 20.18, 14.14, 14.03.
20. General procedure for preparation of dihydroquinazoline-benzodiazepine tetracycle 26: To a
2.0-5.0 mL microwave vial was added a solution of butyraldehyde (246 μl, 1.350 mmol) in DCM
(3ml), tert-butyl (2-(aminomethyl)phenyl)carbamate (300 mg, 1.350 mmol), and MgSO4. The
reaction was sealed and irradiated for 10 minutes at 120°C to yield the Schiff base in quantitative
yields (Rf 0.82, 25% EtOAc/Hex). n-Butylisocyanide (143 μl, 1.350 mmol) and 2-((tert-
butoxycarbonyl)amino)benzoic acid (320 mg, 1.350 mmol) were added and reacted at 120°C
under microwave irradiation. The crude mixture was poured into a separatory funnel containing
saturated sodium bicarbonate and DCM. The organic layer was collected, dried, loaded onto 2 g
silica gel and purified on a Biotage Isolera (40g column, gradient 10%-35% EtOAc/Hex) to yield
the Ugi product (478 mg, 0.783 mmol, 58 % yield). The Ugi product was then taken up in 10%
TFA/DCE (5ml), transferred to a 2-5 mL microwave vial and irradiated at 130°C for 20 minutes.
After heating, the reaction was poured into a separatory funnel that contained saturated sodium
carbonate (50 mL) and DCM (50 mL). The organic layer was collected and then the aqueous layer
was extracted twice more with DCM (2×50 mL). The combined organics were dried over MgSO4,
concentrated onto neutralized silica, and purified on a Biotage Isolera (25g neutralized column,
50% EtOAc/2.0% TEA/Hexane) to yield the desire 3,4-dihydroquinazoline-benzodiazepine
tetracyclic product, 7-propyl-7,9-dihydrobenzo[5,6]-[1,4]diazepino[7,1-b]quinazolin-6(5H)-one 27
(87 mg, 0.283 mmol, 21 % yield). 1H NMR (300 MHz, CDCl3): 8.65 (s, 1H), 8.08 (d, 1H, J=7.2
Hz), 7.45 (t, 1H, J=7.2 Hz), 7.2-7.4 (m, 3H), 7.1-7.2 (m, 1H), 7.10 (t, 1H (dd, 2H, J=1.8 Hz,
J=14.7 Hz), 6.95-7.10 (m, 3H), 4.41 (d, 1H, J=13.2 Hz), 4.27 (d, 1H, J=13.2 Hz), 4.12 (t, 1H, 7.5
Hz), 1.8-2.1 (m, 2H), 1.2-1.5 (m, 4H), 0.95 (t, 3H, J=7.2 Hz). 13C NMR (75 MHz, CDCl3):
170.95, 143.533, 137.11, 132.12, 131.64, 129.16, 128.94, 126.07, 125.59, 125.46, 124.48, 122.63,
121.22, 56.41, 43.14, 27.79, 19.42, 14.32.
21. In an exercise to demonstrate uniqueness, virtual libraries for all four scaffolds were enumerated
with Symyx Draw 3.2 (comprising scaffold 1—168 compounds; 2—168 compounds, 3—144
compounds, 4—48 compounds). The parent structure of each compound was then compared with
the 375,000 compounds available in the NIH molecular libraries small molecule repository
(MLSMR) described by pharmacophore fingerprints using PowerMV v0.61. A total of 1043
similar compounds were selected using a Tanimoto Similarity function as implemented in the
nearest neighbor search tool in PowerMV (distance threshold for library 1 and 2 = 0.5; library 3 =
0.29; library 4 = 0.4). The libraries and the MLSMR subset (1571 compounds total) were imported
into MOE (Molecular Operating Environment v2009.11, Chemical Computing Group) and
represented by structural fingerprints (MACCS keys). Tanimoto similarities were computed based
on the MACCS keys, which generated a 1571 by 1571 matrix. The columns of the matrix were
used as input for a principle component analysis and the first three principle components were
represented graphically using MOE (Figure 4).
22. (a) Krasavin M, Busel A, Parchinsky V. Tetrahedron Lett. 2009; 50:5945–5950. (b) Lygin,
Alexander V.; de Meijere, Armin. Org. Lett. 2009; 11:389–392. [PubMed: 19099490]
Dietrich et al. Page 4
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Figure 1.
Representative dihydroquinazoline bicyclic and tetracyclic scaffolds
Dietrich et al.Page 5
Tetrahedron Lett. Author manuscript; available in PMC 2011 July 28.
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