Eosin Y catalyzed difunctionalization of styrenes using O2 and CS2: a direct access to 1,3-oxathiolane-2-thiones

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC00924G, Paper

Arvind K. Yadav, Lal Dhar S. Yadav
An efficient, one-pot, highly regioselective synthesis of 1,3-oxathiolane-2-thiones from styrenes, CS₂, atmospheric O₂ and visible light is reported.

Eosin Y catalyzed difunctionalization of styrenes using O2 and CS2: a direct access to 1,3-oxathiolane-2-thiones

http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC00924G?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Paper

Eosin Y catalyzed difunctionalization of styrenes using O₂ and CS₂: a direct access to 1,3-oxathiolane-2-thiones

Arvind K. Yadav^a and   Lal Dhar S. Yadav*^a  

*Corresponding authors

^aGreen Synthesis Lab, Department of Chemistry, University of Allahabad, Allahabad-211002, India
E-mail: ldsyadav@hotmail.com
Fax: +91 5322460533
Tel: +91 5322500652

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC00924G

Visible light promoted straightforward highly regioselective synthesis of 1,3-oxathiolane-2-thiones (cyclic dithiocarbonates) starting directly from styrenes, CS₂ and air (O₂) is reported. The protocol utilizes eosin Y as an organophotoredox catalyst and clean resources like visible light and air (O₂) as sustainable reagents at room temperature in a one-pot procedure. Additionally, the approach is advantageous in terms of step economy as it skips the prefunctionalization of styrenes to oxiranes, which has been inevitable in commonly used syntheses of 1,3-oxathiolane-2-thiones.


//////////Eosin Y,  catalyzed,  difunctionalization, styrenes,  O2,  CS2, 1,3-oxathiolane-2-thiones

Croatia's Sexiest Beaches

Croatia's main tourist attraction is, and always has been, its beaches. With miles of pristine continental Adriatic seaside and dozens of islands to visit, the sun and fun are endless. For this journey, leave the kids and your inhibitions home; we're taking you to Croatia's 10 sexiest beaches.

10. Zrce Beach (Novalja, Pag Island)

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Located on Pag Island, Zrce Beach is a white-pebbled beach, kissing the crystal-clear Adriatic. It's the only beach in Croatia with the Ibiza party spirit, and droves of locals and tourists flock here looking for a good time. After-hours action at this beach includes 3 popular open-air clubs; Aquarius, Papaya and Kalypso offer drink specials, hot DJs, and pools, Jacuzzis and hot tubs. No reason to change out of your bathing suit to party at these hot spots.

9. Hvar Islands (Pakleni, Hvar Island)

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Island-hop from Pag Island to the Hvar, another hot and hip destination for tanned tourists. During July and August, the beaches here are packed which makes for body-bumping parties in the evening. When the sun goes down, head to some of the most popular bars on the Dalmatian coast like Korzo and Carpe Diem.

8. Sv. Jerolim (Sveti Jerolim, Hvar Island)

Mlc, via Wikimedia Commons CC-BY-SA-3.0

Don't leave the Hvar Islands just yet. Sv. Jerolim on Sveti Jerolim's coast, is isolated and beautifully preserved. A well-known nude beach, this isn't the place to go for large parties and a swinging singles' scene, but it is the perfect hideaway for you and someone special. There are a few restaurants on the beach and outdoor showers to wash away the day's heat.

7. Zlatni Rat (Bol, Brac Island)

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Zlatni Rat beach is home to a spectacular sandbar known as the Golden Horn. The bar is 580 yards long and provides this beach with a unique shape and unparalleled people-watching. The beach offers restaurants, cafes and a surplus of water sports. The nightlife is more relaxed than Zrce beach, but there are plenty of open-air bars and nightclubs open for mischief.

6. Kandalora Beach (Frkanj Peninsula, Rab Island)

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Sure, parties and nightclubs are hot, but you can't get any sexier than a nude beach. And Croatia offers these in spades. Kandalora beach is divided into three pebbled and private coves where sunbathers dare to bare it all. There's a small fee to enter these beaches, but the coves are easily reachable if you're dropping anchor in the Adriatic.

5. Valalta Resort (Rovinj)

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If you're looking to add a little romance to your Croatian vacation, Valalta Resort near Rovinj is a perfect destination. Accommodations here include fully equipped apartments, luxurious caravans and intimate bungalows. The beach stretches for about three miles and offers many sandy and stone bays perfect for nude sunbathing.

4. Brela Beach (Vrulja)

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Brela Village is a Mediterranean dream; miles of white beach lined with fig trees and olive groves. Brela is the home to some of the most beautiful beaches in Croatia, with nearby Vrulja Cove topping the list. A desirable location for couples, it's best reached by boat and encourages swimming and sunbathing au naturale.

3. Baska Beach (Krk Island)

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Krk Island is the largest Croatian island and is located in the picturesque Kvarner Bay. The must-see destination on Baska is the Vela Plaza, or Great Beach, where bars, restaurants and cafes offer a reprieve from the sun. The Great Beach is the place to be seen, but Baska beach also offers plenty of coves for those seeking a more intimate experience.

2. Girandella Beach (Rabac, Istria Island)

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Once a quiet fishing village, Rabac is now a bustling tourists' resort with a spirited nightlife. At Girandella Beach, unique rock and jetty formations make diving very popular during the day. At night, the partying takes place right on the beach, where DJs spin house and techno music. Two summer festivals not to be missed are the Sunrise Festival and the Rabac Summer Festival.

1. Plat Beach (Dubrovnik)

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Number 1 on the countdown is one of Croatia's best-hidden beaches with kicking nightlife. This tiny beach is a balmy oasis of beautiful landscapes. The beach has very little shade, so an umbrella is a must to provide some shelter and a little privacy on the nude beach. In the evening, head to the best restaurants and clubs in Croatia. Click here for a full description of Dubrovnik's nightlife.

UVALA DUBOVICA, HVAR ISLAND, croatia

The Renaissance port of Hvar enjoys a worldwide reputation when it comes to chic bars and racy nightlife. If a good beach is what you’re after, however, it’s best to get out of town. There are several good choices in the coves and bays to the east, of which the most attractive is Uvala Dubovica, a broad pebbly affair beside a historic manor house. The bay’s shallow nature makes it good family paddling territory, although it gets popular with yachts and motorboats in season. Otherwise, difficulty of access tends to filter out the guests – the parking strip on the main road above the bay is only big enough to accommodate about fifty vehicles. Rent a bike or scooter from Luka Rent in Hvar and beach-hop your way along the coast.

Read more: http://www.roughguides.com/article/the-10-best-beaches-in-croatia/#ixzz49GNRpEo5

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1,5-Dimethyl-1H-pyrazol-3-yl Methanesulfonate

 

1,5-Dimethyl-1H-pyrazol-3-yl Methanesulfonate
 

white crystalline solid (mp 88–89 °C) after drying in a vacuum oven:  

¹H NMR (400 MHz, CDCl₃) δ 5.85 (s, 1 H); 3.68 (s, 3 H); 3.25 (s, 3 H), 2.23 (s, 3 H);


¹³C NMR (100 MHz, CDCl₃) δ 152.1, 140.7, 96.3, 37.9, 36.1, 11.3;


HRMS-ESI (m/z) calcd for C₆H₁₁N₂O₃S [M + H]⁺ 191.0485, found 191.0483.

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1,5-Dimethyl-1H-pyrazol-3-ol Hydrochloride

1,5-Dimethyl-1H-pyrazol-3-ol Hydrochloride


BASE IS 



.
 2,3-Dimethyl-3-pyrazolin-5-one; 3201-28-3; 1,5-dimethyl-2,3-dihydro-1H-pyrazol-3-one


 1H NMR OF HYDROCHLORIDE


1,5-Dimethyl-1H-pyrazol-3-ol Hydrochloride, 16

salt 16 (13.7 g, 78% yield) as a white crystalline solid: mp 178–182 °C;\

¹H NMR (400 MHz, CDCl₃)
δ 5.72 (s, 1 H); PYRAZOL 1H
3.65 (s, 3 H); N CH3
2.24 (s, 3 H); PYRAZOL CH3



 1HNMR DISCUSSION

¹³C NMR (100 MHz, CDCl₃) δ 156.6, 146.0, 90.6, 34.1, 10.8;

HRMS-ESI (m/z) calcd for C₅H₉N₂O [M + H]⁺113.0709, found 113.0712.

 13 C NMR PREDICT

///////////////////c1(nn(c(c1)C)C)O

(3Z) -1,1,1- trifluoro-4-methoxy-4- (2-methylphenyl) but-3-en-2-one

 

(3Z) -1,1,1- trifluoro-4-methoxy-4- (2-methylphenyl) but-3-en-2-one

[Step 1] 1- (1,1-dimethoxy-ethyl) -2-methyl-benzene

2 methylacetophenone 5.36g (40mmol), trimethyl orthoformate 5.0g (47mmol), methanol - Le 7.7g (240mmol), and methane sulfonic in toluene solution (100mL) containing sodium sulfate 14.2g (100mmol) and adding an acid 92mg (0.8mmol) was stirred at room temperature for 20 hours. The reaction mixture was diluted with ethyl acetate, washed with a saturated aqueous sodium bicarbonate solution, and dried over magnesium sulfate and concentrated. The crude product was basic silica gel column and purified by (0-10% ethyl acetate / hexanes) to give the title compound 5.5g (76%) I was obtained as a colorless oil. ¹ H-NMR (400MHz, CDCl ₃₎ ^δ: 1.56 (3H, s), 2.46 (3H, s), 3.19 (6H, s), 7.09-7.24 (3H, m ), 7.60-7.68 (1H, m).


 [Step 2] (3Z) -1,1,1- trifluoro-4-methoxy-4- (2-methylphenyl) but-3-en-2-one


 

Reference Examples were synthesized in Step 1 of 8 1- (1,1-dimethoxy-ethyl) -2-methylbenzene 900mg (5mmol), pyridine 790mg of (10mmol) was dissolved in THF (15mL), 0 ℃ to the cooled trifluoroacetic anhydride fluoro acetate 2.1g the (10mmol) we were slowly dropping. After stirring at room temperature for 18 hours, the reaction mixture was washed with 0.1N aqueous hydrochloric acid and diluted with ethyl acetate. The crude product and the organic layer was obtained by drying your concentrated magnesium sulfate and purified by silica gel chromatography (0-10% ethyl acetate / hexanes) to give the title compound 1.0g (82%) was obtained as a colorless oil. ¹ H-NMR (400MHz, CDCl ₃₎ ^δ: 2.22 (3H, s), 3.94 (3H, s), 5.96 (1H, s), 7.11-7.18 (1H, m ), 7.20-7.30 (2H, m), 7.33-7.40 (1H, m). LC-MS, 245 (M + 1).


References 1 http://www.google.fr/patents/WO2010110400A1?cl=en&hl=fr


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1,5-bis(4'-methoxyphenyl)-1,4-pentadien-3-one

Preparation of 1,5-bis(4'-methoxyphenyl)-1,4-pentadien-3-one (Product B)

A solution of p-anisaldehyde (0.61mL, 5.1mmol) and freshly recrystallized 4-(4'-methoxyphenyl)-3-buten- 2-one (0.60g, 3.4mmol) in ethanol (15mL) is prepared in a 100mL round bottom flask. A potassium hydroxide (0.8g) solution in water (20mL) is prepared in a separate beaker. The potassium hydroxide solution is then gradually added to the solution in the round bottom flask over two minutes with continuous stirring for 30 minutes. The solid is extracted by vacuum filtration, followed by water washing. The resulting solid is then dried and recrystallized from ethanol (Figure 6).

Figure 6. Recrystallized 1,5-bis(4'-methoxyphenyl)penta-1,4-dien-3-one (Product B).

Figure 7 depicts the ¹H NMR spectrum of 1,5-bis(4'-methoxyphenyl)penta-1,4-dien-3-one, confirming the loss of the reactive methyl centre in Product A following the reaction with p-anisaldehyde. In this case also, the 2D J-resolved and COSY experiments are used to interpret the downfield resonances between 6.82-8.02ppm (Figures 8 and 9).

Figure 7. ¹H NMR spectrum of 1,5-bis(4'-methoxyphenyl)-1,4-pentadien- 3-one (Product B) in CDCI₃.

The J-resolved spectrum (Figure 8) differentiates 8.6Hz doublet and 16.4Hz doublet, centered at 6.90ppm. It also identifies a 16.0 Hz doublet at 7.73ppm and an 8.9Hz doublet at 7.57ppm further downfield. This data is used to determine the two spin systems in the COSY spectrum (Figure 9), one between 6.90-7.57ppm and the other between 6.90-7.73ppm. The alkene protons on C- 1/C-5 and C-2/C-4 can be allocated as 7.73ppm and 6.90ppm, respectively, while the promatic protons on C-2' and C-3' can be assigned as 7.57ppm and 6.90ppm, respectively. The magnitude of the coupling constants of H-1/H-5 and H-2/H-4 confirms the alkene’s E-geometry.

Figure 8. 2D J-resolved spectrum of 1,5-bis(4'-methoxyphenyl)-1,4-pentadien-3-one (Product B) in CDCI₃.

Figure 9. COSY spectrum of 1,5-bis (4'-methoxyphenyl)-1,4-pentadien-3-one (Product B) in CDCI₃.

1,2-epoxy-4-iodobutane

1,2-epoxy-4-iodobutane




C₄H₇OI
NMR Solvent: CDCl₃





 

Automated VerifyIt Proton Assignments:

Automated VerifyIt Carbon Assignments:

Spectral Data

Additional Data

Download

Type: 13C		Atom No. ⇓ Mult.(coupling const.) Meas. Shift 1 D 52.35960 2 T 0.21127 3 T 36.34340 4 T 46.88940

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