A flexible Pinner preparation of orthoesters: the model case of trimethylorthobenzoate



Dipartimento di Scienze Molecolari e Nanosistemi dell’Universita Ca’ Foscari Venezia, Centre for Sustainable Technologies, calle Larga S. Marta, 2137-30123 Venezia, Italy 
E-mail: marco.noe@unive.it

Green Chem., 2013,15, 2252-2260

DOI: 10.1039/C3GC40774H
Received 24 Apr 2013, Accepted 10 Jun 2013

The Pinner preparation of orthoesters was revisited achieving remarkable improvements. Outstandingly an unprecedented synthesis of trimethylorthobenzoate starting from benzonitrile has been described.
In the absence of additional solvents,
a novel procedure was implemented for the synthesis oftrimethylorthoesters through the Pinner reaction. At 5 °C, the reaction of both aliphatic and aromatic nitriles (RCN; R = Et, Bu, Ph) with a moderate excess of MeOH and gaseous HCl gave the corresponding imidate hydrochlorides [RC([double bond, length as m-dash]NH)OR′·HCl]
in excellent yields (>90%). At 25–65 °C, the methanolysis of alkyl imidate salts provided trimethylortho-propionate and valerate, while only traces of trimethylorthobenzoate (TMOB) were observed. However, the aromatic hydrochloride could be readily converted into the hydrogenphosphate salt [PhC([double bond, length as m-dash]NH)OR′·H3PO4] which, in turn, underwent a selective (>80%) reaction with MeOH to produce TMOB in a 62% isolated yield. This allowed for an unprecedented Pinner-type synthesis of TMOB starting from benzonitrile, rather than from the highly toxic trichloromethylbenzene. Overall, remarkable improvements in safety and process intensification were achieved.

Large-ring lactones from plant oils


Timo Witta and   Stefan Mecking*a  
Chair of Chemical Materials Science, University of Konstanz, Department of Chemistry, Universitätsstraße 10, 78457 Konstanz, Germany 
E-mail: stefan.mecking@uni-konstanz.de ;
Fax: +49 7531 885152 ;
Tel: +49 7531 882593
Green Chem., 2013, Advance Article

DOI: 10.1039/C3GC40905H
Received 15 May 2013, Accepted 11 Jul 2013
First published online 29 Jul 2013
A synthesis route for macrocyclic compounds such as lactones starting from common plant oils has been developed.
Large-ring lactones from plant oils

Large-ring lactones and lactams were prepared utilising the full fatty acid chain of common plant oils as a source of the macrocycle. Ring closure via acyloin condensation does not require large volumes of solvents for dilution. Nonadecalactone (NDL) and tricosalactone (TCL) can be converted to novel polyesters by ring opening.

Watermelon Juice Prevents Aching Muscles Food Chemistry: The amino acid L-citrulline found in the fruit could help athletes avoid muscle soreness after a hard workout

Photo of watermelon juice smoothie in tall glass

The Next Sports Drink?
Watermelon drinks, like this smoothie, could help cut down on muscle soreness after intense exercise.
Credit: Shutterstock
Before taking a long bike ride on a hot summer day, have some watermelon: The juicy fruit may ward off muscle pains. Researchers report that people who drank watermelon juice before exercising felt less sore the next day than those who drank a pink placebo beverage (J. Agric. Food Chem. 2013, DOI: 10.1021/jf400964r). They also found that cells absorb the presumed active ingredient, L-citrulline, more readily from unpasteurized watermelon juice than from plain water spiked with the compound, suggesting the natural source is the optimal delivery


Health benefits of  Bioflavonoids for Anemia

Holistic health. Bioflavonoids. Vitamin P. Vitamin C. Ayurveda. Ayurvedic philosophy. Happy life. Happiness. Healthy life. Health. Benefits for the heath. Ayurvedic types. Determine your ayurvedic type. Healthy diet. Life without illness. Effective treating. Natural healing. Harmony.
What are the Bioflavonoids?
Scientists have found that bioflavonoids have specific capabilities to increase bodily health in many different ways. They support strong cell formations and, according to some medical services, even suppress poor cellular growth in order to deliver an anti-carcinogenic effect. Bioflavonoids contribute to good heart health, and combat atherosclerosis, as well as conditions like Alzheimer’s disease. Bioflavonoids are found in many of the same foods that contain vitamin C, an essential nutrient for the daily diet, and these super antioxidants complement vitamin C, enhancing its effect on the body.
They are the natural pigments in fruits and vegetables. Bioflavonoids are also referred to as “vitamin P”, are super-antioxidants found in many natural foods. New scientific researches found that bioflavonoids help maintain capillaries. Capillaries are microscopic blood vessels that allow the oxygen, hormones, nutrients, and antibodies to pass from the body’s bloodstream to individual cells (body organs). If a capillary’s walls are too fragile they will allow blood to drain out of the vessels and into the cells. The result of this is easy bruising, brain and retinal hemorrhages, bleeding gums and other abnormalities.
Bioflavonoids in recent studies also have been shown to help the blood clot, this alone can be helpful in treating phlebitis and other clotting disorders. Many bioflavonoids prevent the cellular damage caused by free radicals; these are unstable molecules that are formed when the body burns oxygen.
Today 40 % of people in the world suffer from anemia. The reason lies in the diet. Unbalanced food is a global problem of modern society.
Nowadays, a person needs rather less than 3000 kcal /day to cover energy costs, whereas only 50-100 years ago energy consumption was 6000 kcal, so now it is sufficient 2 times less food to cover the energy.
Modern food provides our energy consumption, but it does not provide our body with essential vitamins, minerals, dietary fiber, other micronutrients that are of a very small amounts in today’s food.
At the beginning of XX century an important vitamin C was discovered.
A little later in plant foods bioflavonoids (plant polyphenols) were discovered.
It was found that these substances enhance the action of vitamin C, and without them it is ineffective. But the main thing is that these substances reduce the permeability and capillary fragility. Thus, vitamin P got his name from the Latin. Permeability.
It is said that: “The age of a man – it is the age of his capillaries”.
Of course, this statement is too categorical. Yet it is a a need of correct understanding of the importance of the capillary system to maintain a healthy and active lifestyle.
It is believed that the system of blood vessels is a set of arteries and veins in which the heart pumps blood. This view is generally correct, but at the same time deeply flawed. Figuratively speaking, the arteries and veins – are just pipes of different diameters by which the blood flows. With regard to the capillaries, which bind them into a single circulatory system. It is a hundred thousands of kilometers of health with the area of more than 6000 square meters This is the length of the capillaries in the human body, in fact it is a huge endocrine system. Near 30-50% of our blood flows in capillaries and if they narrow the blood goes to veins and arteries which leads to the raising of the arterial pressure.
Violations in the capillary network is the main cause of almost any disease process. They are the basis of heart disease, metabolic disturbances, lead to stagnation processes, coronary artery disease, heart attacks, strokes, etc.
Heart pumps blood, arteries and veins pass it in the right direction, but the capillaries provide the normal functioning of cells, including heart muscle.
Capillaries are tiny blood vessels in it, permeates all of our tissues and organs.
They supply the cells with oxygen and nutrients, remove waste products from them. It is on the border of the cell and the capillary the metabolism takes place.
Capillaries consist of only one layer of cells that are “glued” by elastic fiber protein called collagen. For its reproduction sulphur and vitamin C is required, which also requires “helpers” in the form of bioflavonoids.
A prominent Russian biologist, zoologist and protozoologist, best remembered for his pioneering research into the immune system  Élie Metchnikoff, who received theNobel Prize in Medicine in 1908, shared with Paul Ehrlich, for his work on phagocytosis. He is also credited by some sources with coining the term gerontology in 1903, for the emerging study of aging and longevity.
So, once Élie Metchnikoff was attracted by some of the products that are produced in the gut with the decay of proteins. It turned out that the failure of self-purification system leads to their accumulation and self-poisoning (toxicity) of the body, causing changes in respiratory system, heart rate changes, convulsive reaction etc.
The environmental situation is deteriorating with each passing year. Chemical hazards has become an important factor in human ecology.We are not talking about acute poisoning, but a permanent chemical stimuli.. Each day with food, water and air our body consumes foreign substances (xenobiotics), which are not used in the normal processes of life. These are flavors or preservatives, synthetic drugs and dyes, exhaust fumes, tobacco smoke etc.
Bioflavonoids help us by reducing the permeability of capillaries, so bioflavonoids impede these chemical substances distribution and access into our vital body organs. Increasing hazard on our body systems requires regular cleansing and increased intake of bioflavonoids, especially children, because they are most exposed to various unfavorable factors.
Giant Endocrine System
According to scientific predictions, by 2025 year one third of the adult population of our planet will suffer from high blood pressure. Already, cardiovascular diseases cause about 30% of all deaths.
Recent studies conducted in several countries, showed that the factors of modern life leads to intense formation in the capillaries the substance called endothelin-1, which causes narrowing of the capillaries, thus making high blood pressure.
Capillaries are not just tubes to supply oxygen and nutrients, but a giant endocrine system of capillary network.
It is proven that the red pigments of dark grapes, black currants, and other foetus, of so-called anthocyanins (from the Greek. “Antosii” – a flower, “cyan” – blue), has powerful capillary strenghtening action and also inhibits the formation of endothelin-1, preventing the narrowing of the capillaries and high blood pressure. Their lack in food is one of the main causes of hypertension.
Hard mental and physical work, stresses, pregnancy and childbirth, excessive food consumption is accompanied by oxygen deficiency (hypoxia). It is a constant companion of anemia, atherosclerosis, hypertension, coronary heart disease and brain etc.
Ability to perform a variety of loads depends on the respiratory and cardiovascular systems. For example, if your heart increases load, a sharp discrepancy between the demand of the heart for oxygen and its delivery may lead to coronary insufficiency, apnea, cardiac arrhythmias.
Accumulated with age malfunctions of the capillary system, so even small loads cause a lack of oxygen. Therefore, physical activity objectively characterize the degree of tissue oxygen supply (hypoxic status of the organism). Experimentally proved the link between lifespan and resistance to oxygen starvation.
Thus, the health of the capillaries is a key indicator of our health, which depends on the use of vitamin P.
Over the last 15-20 years, consumption of bioflavonoids decreased significantly. We consume less natural plant foods which contain vitamin P, moreover in many foods the amount of these important substances is reduced to increase shelf life.
As a result, we got a massive vitamin deficiencies and significant deficiency of vitamin P – the only vitamin that has capillary strenghtening action.
The most recent scientific breakthroughs confirm that these powerful nutrients are an important part of a healthy diet. Studies from around the world support the fact that diets high in bioflavonoids are associated with lower incidences of most diseases. Along with other phytonutrients, the health benefits of bioflavonoids are one reason why the National Institutes of Health and the U.S. Surgeon General’s office advocate the intake of several servings of fruits and vegetables every day. Powerful, health-promoting nutrients from nature – the virtues of plants will never cease to amaze us.
Fresh fruits and vegetables are generally the top choices for getting plenty of bioflavonoids in a diet. Here are some of the most popular ways to get the most of these helpful nutritional elements.
                                                        Bioflavonoid Superstars:   
1. Red Bell Peppers or Sweet Peppers – Red peppers contain three times more vitamin C than orange juice, according to some medical sources. Scientists agree that raw bell peppers are an effective way to get bioflavonoids into the system.
2. Strawberries – these luscious red berries are a great source of bioflavonoids. Other berry types are similarly rich in these kinds of antioxidants. This leads to specific claims of health benefits for berry-made wines and derivative foods.
3. Citrus Fruits – Oranges are a significant source of bioflavonoids. Lemons and limes, as well as peaches, nectarines and other fruits all contain vitamin C and bioflavonoid superoxidants.
4. Grape seed extract – has beneficial effects on the circulatory system. Some of these include improvements to cardiovascular health, protective antioxidant effects, improved eye health, and anti-inflammatory action.
5. Black currants – have a very high content in antioxidants and vitamins. In particular, they’re very rich in Vitamin C. Black currants also contain several rare nutrients, like GLA ( Gamma Linoleic Acid, a very rare Omega-6 essential fatty acid) and MAOI (Monoamine Oxidase Inhibitors), and may therefore be used in therapies against depression.
6. Lingonberry or Cowberrycontain plentiful organic acids, vitamin C, provitamin A  (as beta carotene),  B vitamins (B1, B2, B3), and the elements potassium, calcium, magnesium and phosporus.  In addition to these nutrients, they also contain phytochemicals that are thought to counteract urinary-tract infections, and the seeds are rich in omega-3 fatty acids.
7.  Broccoli – this green vegetable has a lot of vitamin C, as well as some other essential vitamins for a healthy diet. As with other foods, use broccoli raw for best results.
8. Brussels Sprouts – for a hearty meal, include these cabbage type sprouts. Rich in antioxidants, they are also packed with their own unique taste for a delicious way to get bioflavonoids and vitamins.
9. Tropical Fruits – exotic fruits, like mangoes and papayas, have a lot of bioflavonoids and other nutritional elements packed under their skins. Don’t miss out on what they have to offer.
10. Garlic – by most accounts, garlic is a superfood. Our food culture has long been aware of its anti-inflammatory properties, but now scientists are counting it as among the natural foods rich in bioflavonoids, and therefore able to deliver the antioxidant values we associate with “healing foods.”
11. Spinach –this magic plant has all of the qualities you would associate with a green vegetable rich in antioxidants. Spinach is a good all-purpose nutrient – try it in place of lettuce for a salad that’s bursting with nutrition.
12. Teas – Green tea/ Rooibos/ Hawthorn – are known to have a lot of powerful elements that contribute to longevity and good health. Green tea extract plays a beneficial role in protecting against certain infections, improving cardiovascular health, promoting better dental hygiene, and offering protection from the development of some types of cancer.Traditional medicinal uses of rooibos tea in South Africa include alleviating infantile colic, allergies, asthma and dermatological problems.
These are just some of the top producing fruits and vegetables that deliver bioflavonoids and vitamin C to the table. Vitamin rich foods are always more effective in their raw form, look for colorful, fresh fruits and vegetables to benefit from a diet that will contribute to your health in many ways.

If we speak about the problem of anemia, and how to cure it. These natural medicine will be beneficial: clover, nettle (which withdraws water from kidneys, thus cleaning it), spinach, celery, parsley, dill, lettuce, ramson, garlic, sorrel, spring onions, longan fruit, pomegranates etc.
Longans are known to replenish blood and are excellent cure for anemia. They are also known to boost iron absorption in the body. Longans are also known to lower the risk of certain types of cancer and boost cell production.
One study found that pomegranate juice contains more polyphenols than red wine, grapes, and acai juices. Additional, but limited research, suggest pomegranate juice as a helpful supplementation to fighting LDL (harmful) cholesterol oxidation.

Among Herbs, which can provide you with bioflavonoids are: Shatavari, Gotu Kola, Arjuna, Ginkgo, Gambhari etc.

Natural Remedies for Ulcerative Colitis

New Drug Approvals


Written by Michael Sapko for drugs.com

There are a number of medical treatments available to manage ulcerative colitis. Modern therapy is targeted at preventing flares and inducing remission (at least temporarily). These medications, however, have serious side effects, especially when taken for long periods. Corticosteroids, for example, can cause a number of cosmetic, psychological, and hormonal problems. Many patients simply cannot tolerate these medications. Children have particular problems with standard medications. When compliance with prescribed medicines is poor, treatment failure is common.1,2 Thus, many patients turn to natural remedies for their ulcerative colitis..http://www.drugs.com/health/ulcerative-colitis/natural-remedy-1234/#1

Some herbal or organic remedies may help promote gut health and prolong the time between remissions (flares).

  • Dietary modification includes elimination of food allergens and optimizing living conditions. A relatively high proportion of Europeans (either primary or of European descent) have an allergy to gluten, a substance found…

View original post 50 more words

J&J’s Simponi Aria gets approval by the FDA for the treatment of rheumatoid arthritis

July 19 2013 | By Márcio Barra

The FDA has approved an intravenous formulation of the tumor necrosis factor inhibitor Simponi Aria (golimumab)for the treatment of moderate to severe rheumatoid arthritis in combination with methotrexate, according to manufacturer Janssen Biotech. This makes it the fourth approval for the drug since its initial approval in 2009, making it a strong contender for blockbuster status. The drug is already approved for active psoriatic arthritis, active ankylosing spondylitis, and moderate to severe ulcerative colitis unresponsive to previous treatments, the latter back in May 2013.

View original post 272 more words

Greening hydrogenation catalysts

Iron nanoparticles

Researchers in Canada and Japan have worked together to develop a novel iron catalyst, which they suggest might make hydrogenation reactions more environment friendly. Hydrogenation reactions are commonly catalyzed using palladium or platinum compounds, but these metals are rare and expensive posing significant economic and environmental problems in obtaining adequate supplies. Iron would make a good substitute as it is abundantly available. But, iron oxidizes. Writing in the journal Green Chemistry, the team from RIKEN and McGill University, have embedded iron-based catalyst nanoparticles in a polymer matrix to protect them from oxygen and water and so preclude their catalyst from rusting. “Our aim is to develop iron-based catalysts not only for hydrogenation but also a variety of organic transformations that can be used in future industrial applications,” explains RIKEN researcher Yoichi Yamada.

New iron catalyst promises green future for hydrogenation


  • Reuben Hudson, Go Hamasaka, Takao Osako, Yochi M. A. Yamada, Chao-Jun Li, Yasuhiro Uozumi, and Audrey Moores. Highly Efficient Iron(0) Nanoparticle-Catalyzed Hydrogenation in Water in Flow, Green Chemistry. doi:10.1039/C3GC40789F



New Drug Approvals

All about Drugs, live, by DR ANTHONY MELVIN CRASTO, Worldpeaceambassador, Worlddrugtracker, OPEN SUPERSTAR Helping millions, 100 million hits on google, pushing boundaries,2.5 lakh plus connections worldwide, 36 lakh plus VIEWS on this blog in 225 countries, 7 CONTINENTS The views expressed are my personal and in no-way suggest the views of the professional body or the company that I represent, ........................A 90 % paralysed man in action for you, I am suffering from transverse mylitis and bound to a wheel chair, With death on the horizon, I have lot to acheive

madame scientist's not-so-mad musings

Just another WordPress.com site

Her Island Kitchen

Hourushaa Dowlut

Bombay Dak

A man from Bombay, who lives in Bangalore, and writes about India.

Ferreira Lab, University of Georgia

Synthetic Methods, Natural Product Synthesis | Twitter: @TheFerreiraLab


Green Chemistry Awesomeness.


Experiencing India, 2013

Joys & Woes of a Karachiite

About life in Karachi - As experienced by a Pakistani



Pharmaceutical Regulatory Practices (3PR101)

Dr. Charmy Kothari, Course Coordinator


Just another WordPress.com site

Global Regulatory Affairs (3PR202)

Dr. Charmy Kothari, Course Coordinator


Bring On The Chef In You

The other Iran

A site about the people of Iran. Please enjoy and share with others.

Pharmaceutical Analysis III

The greatest WordPress.com site in all the land!

%d bloggers like this: