Cyclopropanes in water: a diastereoselective synthesis of substituted 2H-chromen-2-one and quinolin-2(1H)-one linked cyclopropanes

Green Chem., 2016, Advance Article
DOI: 10.1039/C5GC02443A, Paper

Ashish Anand, Jayashree Yenagi, J. Tonannavar, Manohar V. Kulkarni
A one-pot three component reaction has been developed for the synthesis of substituted cyclopropanes employing 4-bromomethyl-2H-chromen-2-one/quinolin-2(1H)-ones, aromatic aldehydes and activated nitriles.

A one-pot three component reaction has been developed for the synthesis of substituted cyclopropanes employing 4-bromomethyl-2H-chromen-2-one/quinolin-2(1H)-ones, aromatic aldehydes and activated nitriles. The room temperature reaction in aqueous medium has been found to be diastereoselective and high yielding.

http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C5GC02443A?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

2-(6-Methyl-2-oxo-2H-chromen-4-yl)-3-phenyl-cyclopropane-1,1-dicarbonitrile (4a)
4a, (R= -H, R’= 6-CH3, R”= -CN, X=O)

For a typical compound 4a, (R= -H, R’= 6-CH3, R”= -CN, X=O) IR spectrum showed band at 2246 cm-1 (cyanide) and 1720 cm-1 (lactone). Further, the formation of cyclopropane ring was confirmed by the 1H-NMR wherein the C5-H of coumarin ring resonated at 7.83 ppm as a doublet with 5JC5-H = 1.2 Hz showing a 5-bond coupling with the C4-CH of coumarin ring. C4- CH of coumarin ring appeared at 4.83 ppm as doublet of doublets with Jvic(CH) = 8.8 Hz, Cou-CH 5JC5-H = 1.2 Hz. CH attached to aryl group resonated at 4.61 ppm as a doublet with Jvic(CH) = 8.8 Hz. C6-CH3 protons appeared at 2.45 as a singlet. C3-H was observed as a singlet at 6.82 ppm. Other aromatic protons resonated between 7.68-7.41 ppm. In 13C-NMR, the carbon attached to two cyano group resonated at 15.08 ppm, the methyl carbon appeared at 20.55 ppm. Cyclopropane ring carbon attached to aryl group resonated at 32.81 ppm whereas the one attached to coumarin appeared at 36.78 ppm. Carbon of two cyano group resonated at 112.68 and 112.91 ppm. The lactone carbon of the coumarin ring appeared at 159.35 ppm. Aromatic carbons resonated in the range of 112-159 ppm. Formation of the product was further confirmed by EI-MS where the molecular ion peak was observed at 326 m/z

 

 2-(6-Methyl-2-oxo-2H-chromen-4-yl)-3-phenyl-cyclopropane-1,1-dicarbonitrile (4a) White; Yield 85%; 

m.p: 268-270°C; 

IR (KBr) cm-1 1720 (C=O lactone), 2246 (CN); 

 1H-NMR (400 MHz, DMSO-d6, TMS) δ (ppm): 7.83(d, 1H, 5JC5-H = 1.2 Hz, C5-H), 7.68-7.41(m, 7H, ArH), 6.82(s, 1H, C3-H), 4.83(dd, 1H, Jvic(CH) = 8.8Hz, Cou-CH, 5JC5-H = 1.2 Hz), 4.61(d, 1H, Jvic(CH) = 8.8Hz, Ar-CH), 2.45(s, 3H, -CH3); 

 

 

  13C-NMR (100 MHz, DMSO-d6) δ (ppm): 8.57, 15.08, 20.55, 32.81, 36.78, 45.73, 112.68, 112.91, 115.95, 116.69, 117.64, 124.60, 128.62, 129.00,129.12, 130.90, 133.63, 134.23, 146.64, 151.12, 159.35;    

MS m/z 326(100%); 

 

 

Anal Calcd. for C21H14N2O2 (%), Calcd: C, 77.29; H, 4.32; N, 8.58; found: C, 77.26; H, 4.29; N, 8.55

   Cyclopropanes in water: a diastereoselective synthesis of substituted 2H-chromen-2-one and quinolin-2(1H)-one linked cyclopropanes

Cyclopropanes in water: a diastereoselective synthesis of substituted 2H-chromen-2-one and quinolin-2(1H)-one linked cyclopropanes

Ashish Anand,^a   Jayashree Yenagi,^b   J. Tonannavar^b and  Manohar V. Kulkarni*^a  

*

Corresponding authors

^a

Department of Studies in Chemistry, Karnatak University, Pavate Nagar, Dharwad 580003, India 
E-mail: manohar274@gmail.com

^b

Department of Studies in Physics, Karnatak University, Pavate Nagar, Dharwad 580003, India

Green Chem., 2016, Advance Article

DOI: 10.1039/C5GC02443A http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C5GC02443A?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract   http://www.rsc.org/suppdata/c5/gc/c5gc02443a/c5gc02443a1.pdf /////////////////////////  c1(ccc4c(c1C2[C@@H](C2(C#N)C#N)c3ccccc3)\C=C/C(O4)=O)C        Seychelles

Seychelles - Wikipedia, the free encyclopedia

en.wikipedia.org/wiki/Seychelles

The Seychelles was uninhabited throughout most of recorded history. Some scholars assume that Austronesian seafarers and later Maldivian and Arab traders ...

‎Seychellois Creole people - ‎James Michel - ‎Victoria - ‎Seychellois Creole

 website www.seychellesbookings.com

Young Coco de mer Palms at the Vallee de Mai natural reserve, a UNESCO Heritage site, on Praslin island, Seychelles

A Coco de mer palm at Vallee de Mai forest, a UNESCO World Heritage site, in Praslin island, Seychelles

Alphonse Island, Seychilles, Africa

Enjoy a remote escape on this private island off the coast of Africa. “It has a population of 82, so it is guaranteed not to be crowded!” says Terrance Zepke, author of The Encyclopedia of Cheap Travel.
Getting there: Take a 50-minute flight from the larger island of Mahé.
What to do: Experience some of the best diving and fishing in the world; explore the Alphonse lagoon by canoe; or go sailing on the Indian Ocean.
Where to stay: There is one hotel on the island, Alphonse Resort; it features 25 chalets and 5 executive villas. Rates start at $375 per night.

SEYCHELLES – Tortoises, pirates and erotic nuts in the lost continent

Text and images © marcus karlsen / no use without written permission
Four degrees south of the equator lies one of the world's most beautiful archipelagos. The Seychelles consists of 115 stunning secluded islands in the Indian Ocean.

Anse Source d'Argent, La Digue, Seychelles.

The Seychelles has pristine beaches, green palm forests, turquoise waters and lots of charm. Here you can tuck yourself away on a romantic honeymoon, walk in beautiful scenery, jump in the crystal clear sea and explore a colourful world - or simply relax on the white sandy beaches.
The name is familiar, but the islands are still an unknown jewel for many. The islands belong to the former Gondwanaland, the lost continent that included Africa, Madagascar and India. We find them off the east coast of Africa and Madagascar. The former French and British colony became an independent country only in 1976. The people on the island are like a box of mixed candy. Most are descendants of European colonists, African slaves and Indian or Chinese merchants. Their skin colour is everything from light to dark brown, their hair blonde to black and their eyes blue, green or brown. What they all have in common is that they are never in a hurry, they always have time for a chat or a smile.
Forest Erotica on Praslin
When God created Adam and Eve he probably used the Coco de Mer palm tree on the island of Praslin as a template. The palms coconut is the world's largest and shaped like a woman's abdomen and the trees male flowers resemble the man's private parts. When sailors in the 1700s discovered the erotic nuts after months at sea, it is said that they went completely bananas.

The world's largest coconut, Coco de Mer, Valle de Mai, Praslin, Seychelles.

The flower of the Coco de Mer, Valle de Mai, Praslin, Seychelles.

The National Park Vallee de Mai is a UNESCO World Heritage Site. The amazing palm tree Coco de Mer, which reaches 30 meters into the air and has nuts that weigh up to 30 kilograms, is found only on the Seychelles. No one had seen the trees when the first nuts were washed up on distant beaches, thus the legend of the underwater palm tree, Coco de Mer – the sea coconut. Now you no longer have to look for it at the bottom of the sea, it is easier to take a hike in the national park. In this peaceful little valley we walk through a unique palm forest, a living memory of the forests that once existed when the Seychelles granite islands were still part of Gondwanaland. Millions of years of isolation have led to a unique flora and fauna. Many species are therefore only found here. While we follow the path in the shadows of the huge palm leaves, we keep an eye open for the Seychelles black parrot. A few hoarse cry reveals three black birds who bicker in a tree. Under a giant palm leaf sits a green tree frog, also endemic to the Seychelles.
If you have enough of the unique palm forests of Praslin, you can relax at Anse Lazio, the island's finest beach. When the German travel magazine Reise & Priese's readers named the 12 most beautiful beaches in the world, six of them were located in the Seychelles. Anse Lazio was named the most beautiful - and we know very well why. The coral sand you find here is fine grained and white and the water azure blue. When the rays of the sun shine through the water it is easy to detect the shadows of fish and sea turtles in the crystal clear waters. This mile-long beach is the island's most touristy, but still it is a long way to the neighbours towel. Only a handful of tourists find their way here on a busy day.

The beautiful beach of Anse Lazio, Praslin, Seychelles.

The authorities do not allow beach sellers, so you can enjoy the sound of the ocean uninterrupted. If you want a coral beach all to yourself, rent a car and explore the island. We can guarantee many opportunities to get a beautiful beach all to yourself.
 

La Digue – The island of your dreams
Seychelles fourth largest granite island, La Digue, is perhaps the most beautiful island of them all. It feels as if time has stood still. The first thing that greets you is the ox wagons on the pier.
The small island has only 2,000 residents and a handful of accommodations. On La Digue, simply relax and enjoy the peace and tranquillity that reigns. Rent a bike like everyone else, and discover the beaches with a basket full of swimwear on the rack.

Anse Source d'Argent, La Digue, Seychelles.

  

Granite boulders, Anse Source d'Argent, La Digue, Seychelles.

Seychelles' most photographed beach is Anse Source d'Argent. You will not have this world famous beach all to yourself, but it is so beautiful that you will forget there are other people present. Anse Source d'Argent actually consists of a series of small beaches separated by huge granite boulders shaped by wind and weather in the strangest shapes. Swaying palm trees and tall Takamaka trees provide shade from the burning sun and on the reef you will find fish in all the colours of the rainbow. The calm, turquoise water inside of the reef is 25 degrees Celsius and ideal for swimming, snorkelling or for little kids to splash around in. There is also enough sand to hold a 1 ½ year old busy for days. The beach is many times named one of the world's most beautiful, and most postcards from the Seychelles are from this beach. If you find it hard to leave, do not say we did not warn you. You may be tempted to cancel the return ticket. We spent only two days on La Digue, but would have liked to stay longer.
Curieuse - The tortoise island
The three kilometre long island of Curieuse is known for two things: its many giant tortoises and as a former leper colony. A mile north of the island of Praslin is Curieuse. From 1833 to 1965, the authorities had a special agreement with Mauritius. The lepers from Mauritius were sent here to Curieuse and the mentally ill from Seychelles took the trip to Mauritius. It was assumed that if all lepers were collected on one island, you would get rid of the disease.

Romantic getaway, Curieuse, Seychelles.

Today no lepers are living on Curieuse - only 250 giant tortoises. These were re-introduced on the island in 1980 after they had been exterminated by sailors in the 1800s. The tortoises served as food supply on the sailing ships. After the tortoises were loaded on board, they could survive for nine months without food or water, which meant that the crew had fresh meat for the entire voyage.
Giant tortoises can be several hundred years old and weigh up to 200kg. You can find them only two places in the world, in the Seychelles and on the more famous Galapagos Islands. Curieuse is a national park and can only be visited as a day trip. We travelled with Louis on a boat trip to both Cousin and Curieuse. After several hours at sea it tasted great with grilled tuna and lots of good fruit for dessert.

Giant tortoises can only be found on the Seychelles and on the Galapagos islands, Curieuse, Seychelles.

| Dynax 7D | 17-35mm f/2.8-4.0 (D) | f/4.5 | 1/20s | ISO 100 |

The sea is crystal clear and hundreds of exotic coral fish darts past us as we glide into the water with scuba mask and snorkel. The sky above is blue and the boat is anchored off the tiny island of St. Pierre - a tropical paradise. Yet there is something missing. The Seychelles was once known for its brilliant coral reefs, but below us we only see faded, dead coral. Louis says that almost all corals down to 10 meters are dead, victims of global warming and the El Niño. We can see the effect on several beaches in the country. Bits of dead coral are washed ashore by the waves. Fortunately corals are now starting to come back and Louis eyes a hope that the reefs someday will be as they once were.
Cousin - Bird Paradise
The entire island of Cousin is a nature reserve, and to keep rats and other animals away from it we can only go ashore with the park authorities little boat. The small boat ploughs through the crystal clear waters. Below us we see the shadow of a ray that glides slowly across the sandy bottom. The boat is moving at full speed towards the beach at the bird island of Cousin. There is no jetty, so the boat sails right on to the fine sandy beach. The blue sky above the island is full of seabirds. Lightning fast frigate birds plunge down to steal food from the dutiful tropicbirds which have been out at sea fishing. Birds and animals have no natural predators on the island and they are not afraid of humans.

Coming ashore, Cousin, Seychelles.

From a few feet away, we can see how the fairy terns nest in the branches above us. The fairy tern makes no nest, but lays its eggs directly on a branch. Here it lies balancing until it hatches and a small downy young chick emerges. At the foot of the trees nests the white tropicbirds and everywhere there are small lizards and geckos. The island has the world's highest density of lizards, so be careful where you put your foot. Before you know it, a little lizard is wriggling under it. No dangerous animals live here, but watch out for George. He is a big giant tortoise who is looking for tourists to get his neck scratched.
  

Fairy terns, Cousin, Seychelles.

Treasure Hunting on MAHÉ.
Modern treasure hunters are coming to the Seychelles for entirely different reasons than the legendary pirates of the past. Now it's white, sandy beaches and the tropical paradise that beckons. When the infamous pirate Olivier Levasseur, known as "La Buse" was finally taken and hung on Reunion Island in 1730 it is said that he threw a piece of paper out in the crowd and shouted "Find my treasure if you can ... ".
A cryptogram that belonged to an old Norwegian whaler and strange characters on the rocks in Bel Ombre on the island of Mahé has led many treasure hunters here from near and far. Most of the area is therefore turned upside down by treasure hunters looking for gold and gemstones. So far, they have only found a few gold coins and some old weapons.
90 per cent of the 81 000 inhabitants of the Seychelles live on the main island of Mahé, which includes the capital city of Victoria. Tourists tend to gather in Beau Vallon where the offer of restaurants, hotels and activities are numerous. If you want action and activities Beau Vallon is your place in the Seychelles. The beach is not the country's finest, but you can kayak, wind surf, jet ski or scuba dive at Shark Bank. In September and October, this is one of the best places to snorkel with whale sharks. The world's largest fish can grow up to 15m long and weigh 12 tons, but it eats only plankton and is therefore completely harmless.

Dancing the night away, Beau Vallon, Mahe, Seychelles.

In the early morning hours, you should visit the market in Victoria. Here you will find the everyday life of the islands with sights and smells for everyone. The botanical garden is also worth a visit, or what about a hike in the Morne Seychellois National Park?
They are hanging high and are edible. No, we are not talking about the coconuts, but the bats. How about a bat in a sauce of white wine? At the restaurant La Corsaire in Bel Ombre this is a specialty. So how did it taste? Well, this time we chickened out and left the bats hanging by their feet in the trees, while we enjoyed the delicacies of the sea instead.

Deserted beach, Silhouette, Seychelles.

Annual Kavadi procession through Victoria, capital of Seychelles

Now in its fourth year, the International Carnival Seychelles has started to attract a slew

VICTORIA

 

 

At Mahé, Seychelles.

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