BENZYL VINYL ETHER

Green Chem., 2016, Advance Article
DOI: 10.1039/C5GC02977E, Communication

Ryosuke Matake, Yusuke Adachi, Hiroshi Matsubara
A convenient preparation of vinyl ethers from alcohols with calcium carbide was developed. This protocol is an alternative to the Favorskii-Reppe reaction without any high pressure device.

Synthesis of vinyl ethers of alcohols using calcium carbide under superbasic catalytic conditions (KOH/DMSO)

 LINK       http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C5GC02977E?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

 Vinyl ethers are important and useful synthetic building blocks. Using a test tube with a screw cap, a convenient preparation of vinyl ethers from alcohols with calcium carbide under superbasic catalytic conditions (KOH/DMSO) was developed. The vinylation of primary and secondary alcohols was successfully achieved, affording the desired products in good yields. The gram-scale preparation of a vinyl ether was also demonstrated. In this reaction, calcium carbide acts as an acetylene source, constituting a safer alternative to acetylene gas.

 F. de Nanteuil, E. Serrano, D. Perrotta and J. Waser, J. Am. Chem. Soc., 2014, 136, 6239.


1H NMR

1H NMR PREDICT using nmrdb , signals may vary , use your discretion to understand sequence

13C NMR

13 C NMR PREDICT

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Synthesis of vinyl ethers of alcohols using calcium carbide under superbasic catalytic conditions (KOH/DMSO)

Ryosuke Matake,^a   Yusuke Adachi^a and   Hiroshi Matsubara*^a  

*

Corresponding authors

^a

Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Japan 
E-mail: matsu@c.s.osakafu-u.ac.jp

Green Chem., 2016, Advance Article

DOI: 10.1039/C5GC02977E  ////////////////////   WORLDS BEST BEACHES




1. Le Grottes Plage, Costa Azul, France
Among popular  beaches in the globe, Le Grottes Plage is definitely worth a visit. Dotted with restaurants, this beach is a beach lover’s paradise.




2. Little Beach, Maui
Dotted with volcanic rock formations and dense shrubs, this beach is aparadise and is well known as the ‘unofficial clothing optional beach’.




3. Playa Las Suecas, Contadora Island, Panama
Among nudist beaches in the globe, this is an officialcolony where you are allowed to take off your clothing as and when you desire!




4. Lokrum Island, Dubrovnik, Croatia
A haven for those that love to bathe  this beach can be reached via boats and jetties. Rocky formations and sandy shore make this beach a paradise among nudists.




5. Haulover Beach, Florida, USA
This beach is counted as number five in this list of most popular beaches in the world because of its exotic beauty that enthralls its  bathers that come here to sun bathe in their most natural form.






6. Hedonism II, Negril, Jamaica
With a white sandy shoreline stretching 7 miles, this beach is a holiday maker’s Mecca and is visited, both by couples and families. It’s a passionate place where you can indulge in fulfilling many of your desires! Wink…Wink!




7. Black’s Beach, San Diego, United States
If visiting USA, make a visit to Black’s Beach that is one of most famous and beautiful beaches in the whole of United States. It is also a surfer’s paradise.




8. Montalivet Beach, France
The beach is famous for its  beach resort, the very place where international naturist movement started and boasts of 1800 campsites where you can take your clothes off and chill out.


9. Abrico Beach, Rio de Janeiro, Brazil
A bare all beach, it attracts nude bathers from all quarters of the globe. One can take part in a number of fitness programs here.


10. Club Orient, St. Martin, Caribbean
It is a famous resort and is counted among the world’s best  beaches simply because of its picturesque location and the presence of casinos and shopping arcades that make it a fun spot for tourists.



11. Arambol Beach, Goa, India
Armabol is a nudist’s favorite beach in India and is dotted with a rocky terrain and smooth waters.




12. Red Beach, Matala, Greece
When writing about world’s best  beaches, mention must be made of this exotic beach that used to be a haven for hippies in the late 60’s. Dotted with caves and ruins, this beach surely will enthrall all of you with its pristine beauty.



Image Credit: googleusercontent
13. El Torn Beach, Tarragona, Spain
Most popular among nude activists and lovers, this beach is one of the best beaches in Spain as bathers here can roam around wearing just about nothing, without having to give anyone an explanation!


14. Samurai Beach, Tomaree National Park, Australia
Drive down the beautiful Pacific Motorway, north of the capital city of Sydney to reach this awesome beach that is a hub for nude bathers that come here to play sports like volleyball and tug of war.


15. Plakias Beach, Crete, Greece
Plakias is Crete Island’s biggest beach that attracts  bathers and scuba divers from all across the planet.


16. Praia do Pinho Beach, Brazil
This beach is located in Santa Catarina and opened its doors to the nudists way back in 1987. From this beach, you can visit the world famous stature of Christ known as Cristo Luz.

Image Credit: travelchannel


17. Wreck Beach, Vancouver, Canada
The beautiful beach stretches to more than 7.8 km in length and is one of the world’s best beaches that is now counted as one of the seventh wonders of Canadaaaronvonhagen.




18. Spiaggia di Guvano, Corniglia, Italy
this beach can be reached once you cross the many caves that flank the shores.




19. Baker Beach, San Francisco, USA
San Francisco isn’t merely famous for its Golden Bridge, but attracts visitor to its rocky beach that offers majestic views of the bridge and is also a heaven for nude bathers. But it is only towards the end of the northern portion of this beach that you can sun bathe in the nude.






20. Moshup Beach, Massachusetts, USA
Known for its Bohemian styled sun bathers that come here to bathe and tan, this beach is accessible to nudists as well as others.







//////
 

The ¹H and ¹³C NMR chemical shifts of 48 industrially preferred solvents in six commonly used deuterated NMR solvents (CDCl₃, acetone-d₆, DMSO-d₆, acetonitrile-d₃, methanol-d₄, and D₂O) are reported. 

This work supplements the compilation of NMR data published by Gottlieb, Kotlyar, and Nudelman ( J. Org. Chem. 1997, 62, 7512) by providing spectral parameters for solvents that were not commonly utilized at the time of their original report. 

Data are specifically included for solvents, such as 2-Me-THF, n-heptane, and iso-propyl acetate, which are being used more frequently as the chemical industry aims to adopt greener, safer, and more sustainable solvents. These spectral tables simplify the identification of these solvents as impurities in NMR spectra following their use in synthesis and workup protocols.

Over the past decade, there has been an increasing focus on the application of green chemistry principles throughout the chemical industry. A key component in the development of sustainable chemical processes is solvent, which constitutes approximately half of the mass used in the manufacture of active ingredients.(1) Further emphasizing the importance of solvent choice, one of the 12 Principles of Green Chemistry outlined by Anastas and Warner(2) specifically focuses on the use of safer solvents whenever possible. The implications of solvent selection are also aligned with those principles that encourage the use of more benign chemicals and renewable feedstocks. For example, bioderived solvents, or those that have life cycle advantages, can offer sustainability benefits over more conventional solvents.(3) Several pharmaceutical companies have published solvent selection guides to enable chemists to choose more sustainable solvents, with an emphasis on safety, health, and environmental impact.(4) In an attempt to align the recommendations of the various institutions and encourage the incorporation of these industrially preferred solvents into chemical research, a comprehensive evaluation of all of the solvents was published by the Innovative Medicines Initiative (IMI)–CHEM21(5) in 2014.(6)

Since their publication in 1997, the tables of chemical shifts found in NMR Chemical Shifts of Common Laboratory Solvents as Trace Impurities by Gottlieb, Kotlyar, and Nudelman have been an invaluable resource for synthetic chemists to identify residual solvents, e.g., Et₂O or THF, in research samples.(7) An expansion of these data tables to include gases and deuterated solvents commonly used in organometallic chemistry was published in 2010.(8) However, several solvents, such as 2-Me-THF, n-heptane, and iso-propyl acetate, were not widely employed at the time of the original publication but have since been recommended in several solvent selection guides based on their improved safety, sustainability, and/or environmental properties. For example, these recommended solvents often have higher flash points, making them more amenable to chemical processes. One shortcoming, however, is that this reduced volatility can make the removal of residual amounts of these solvents more difficult. In addition, the structures of many of these preferred solvents give rise to complex NMR spectra that complicate the assignment of minor impurity resonances. To simplify the identification of these solvents in NMR spectra and facilitate their adoption into chemical processes, we have compiled ¹H and ¹³C NMR data for 48 solvents discussed in the CHEM21 solvent selection guides.(6, 9) Complete NMR spectral parameters for 29 of these solvents have not been previously reported. The compiled data provided herein will serve as a practical resource when these newer, more preferred solvents are encountered as residual impurities in NMR spectra and, in turn, further advance green chemistry initiatives.

¹H NMR spectral data for industrially preferred solvents in six commonly used NMR solvents (CDCl₃, DMSO-d₆, CD₃CN, acetone-d₆, CD₃OD and D₂O) are provided in Table 1. Solvents in Table 1 were classified as either recommended (green triangles) or problematic (yellow, upside down triangles) in the initial CHEM21 survey.(6) Problematic solvents pose hazards that can typically be managed in a production environment. Solvents that were rated as hazardous were excluded. Additionally, less-classical solvents (e.g., p-cymene, L-ethyl lactate) that scored better than a 7 in both health and environmental categories from the second communication published by CHEM21 were included.(9) Although NMR data for 19 of these solvents were included in either the original report or the 2010 update,(7, 8) data for an additional 29 solvents were obtained. Furthermore, data for previously reported solvents have been modified to include chemical shift ranges of multiplets. Table 2 contains ¹³C{¹H} NMR data for these same solvent impurities. A tabulation of the ¹H and ¹³C NMR data for all 48 impurities in order of chemical shift is included in the Supporting Information to aid in the assignment of unknown peaks.

Table 1. ¹H NMR Data

Table a

Data for these solvents are from refs 7 and 8. Green triangles = Rated as “recommended” in CHEM21 solvent selection guides. Yellow, upside down triangles = Rated as “problematic” in CHEM21 solvent selection guides (see refs 6 and 9).

Table b

Chemical shifts not determined due to reactivity in deuterated solvent.

Table c

Chemical shifts in brackets correspond to −OD isotopomer. See text for more information.

Table d

A second set of resonances was observed for anisole in D₂O: 6.79, t (7.9); 6.50–6.43, m; 3.08, s. See text and Supporting Information for more information.

Table e

1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone.

Table f

Overlapping −OH and −OD isotopomer resonances were observed.

Table g

1:1:1 triplet, J_H–D = 0.8 Hz.

Table 2. ¹³C NMR Data

Table a

Data for these solvents are from refs 7 and 8. Green triangles = Rated as “recommended” in CHEM21 solvent selection guides. Yellow, upside down triangles = Rated as “problematic” in CHEM21 solvent selection guides (see refs 6 and 9).

Table b

Chemical shifts not determined due to reactivity in deuterated solvent.

Table c

Chemical shifts in brackets correspond to −OD isotopomer. See text for more information.

Table d

Solvent was analyzed individually, not in pairs.

Table e

1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone.

This article references 12 other publications.

1. 1.
   

   Jimenez-Gonzalez, C.; Ponder, C. S.; Broxterman, Q. B.; Manley, J. B. Org. Process Res. Dev. 2011, 15, 912, DOI: 10.1021/op200097d
   

   [ACS Full Text ], [CAS]
2. 2.
   

   Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and Practice; Oxford University Press: New York, 1998.
3. 3.
   

   Kerton, F. M.; Marriott, R. Alternative Solvents for Green Chemistry, 2nd ed.; Royal Society Chemistry: Cambridge, UK, 2013.
4. 4.
   

   (a)
   

   Pfizer:

   Alfonsi, K.; Colberg, J.; Dunn, P. J.; Fevig, T.; Jennings, S.; Johnson, T. A.; Kleine, H. P.; Knight, C.; Nagy, M. A.; Perry, D. A.; Stefaniak, M. Green Chem. 2008, 10, 31, DOI: 10.1039/B711717E
   

   [CrossRef], [CAS]

   (b)
   

   GSK:

   Henderson, R. K.; Jimenez-Gonzalez, C.; Constable, D. J. C.; Alston, S. R.; Inglis, G. G. A.; Fisher, G.; Sherwood, J.; Binks, S. P.; Curzons, A. D. Green Chem. 2011, 13, 854, DOI: 10.1039/c0gc00918k
   

   [CrossRef], [CAS]

   (c)
   

   Sanofi:

   Prat, D.; Pardigon, O.; Flemming, H. W.; Letestu, S.; Ducandas, V.; Isnard, P.; Guntrum, E.; Senac, T.; Ruisseau, S.; Cruciani, P.; Hosek, P. Org. Process Res. Dev. 2013, 17, 1517, DOI: 10.1021/op4002565
   

   [ACS Full Text ], [CAS]

   (d) AstraZeneca: Not published, but presented at the GCI- Pharmaceutical Roundtable in 2008. See “Collaboration to Deliver a Solvent Selection Guide for the Pharmaceutical Industry”, by C. R. Hargreaves, and J. B. Manley under publications on the GCI-PR website: http://www.acs.org/content/acs/en/greenchemistry/industry-business/pharmaceutical.html (accessed Jan 15, 2016) .

   (e)
   

   GCI-PR: Document titled “Solvent Selection Guide”, under tools on the GCI-PR website (see above)

   .
5. 5.
   

   (a) http://www.imi.europa.eu; (accessed Jan 15, 2016) .

   (b) http://www.chem21.eu (accessed Jan 15, 2016) .
6. 6.
   

   Prat, D.; Hayler, J.; Wells, A. Green Chem. 2014, 16, 4546, DOI: 10.1039/C4GC01149J
   

   [CrossRef], [CAS]
7. 7.
   

   Gottlieb, H. E.; Kotlyar, V.; Nudelman, A. J. Org. Chem. 1997, 62, 7512, DOI: 10.1021/jo971176v
   

   [ACS Full Text ], [PubMed], [CAS]
8. 8.
   

   Fulmer, G. R.; Miller, A. J. M.; Sherden, N. H.; Gottlieb, H. E.; Nudelman, A.; Stoltz, B. M.; Bercaw, J. E.; Goldberg, K. I. Organometallics 2010, 29, 2176, DOI: 10.1021/om100106e
   

   [ACS Full Text ], [CAS]
9. 9.
   

   (a) Prat, D.; Wells, A.; Hayler, J.; Sneddon, H.; McElroy, C. R.; Abou-Shehada, S.; Dunn, P. J. Green Chem. 2015, 17, 4848, DOI: 10.1039/C5GC90049B
   

   [CrossRef], [CAS]

   (b) Prat, D.; Wells, A.; Hayler, J.; Sneddon, H.; McElroy, C. R.; Abou-Shehada, S.; Dunn, P. J. Green Chem. 2016, 18, 288, DOI: 10.1039/C5GC01008J
   

   [CrossRef], [CAS]
10. 10.
    

    Pohl, L.; Eckle, M. Angew. Chem., Int. Ed. Engl. 1969, 8, 381, DOI: 10.1002/anie.196903811
    

    [CrossRef], [CAS]
11. 11.
    

    Reuben, J. J. Am. Chem. Soc. 1985, 107, 1756, DOI: 10.1021/ja00292a050
    

    [ACS Full Text ], [CAS]
12. 12.
    

    (a) Giuliano, B. M.; Caminati, W. Angew. Chem., Int. Ed. 2005, 44, 603, DOI: 10.1002/anie.200461860
    

    [CrossRef], [PubMed], [CAS]

    (b) Mazzoni, F.; Pasquini, M.; Pietraperzia, G.; Becucci, M. Phys. Chem. Chem. Phys. 2013, 15, 11268, DOI: 10.1039/c3cp50191d
    

    [CrossRef], [PubMed], [CAS]

NMR Chemical Shifts of Trace Impurities: Industrially Preferred Solvents Used in Process and Green Chemistry

Nicholas R. Babij, Elizabeth O. McCusker, Gregory T. Whiteker^*, Belgin Canturk, Nakyen Choy, Lawrence C. Creemer, Carl V. De Amicis, Nicole M. Hewlett, Peter L. Johnson, James A. Knobelsdorf, Fangzheng Li, Beth A. Lorsbach, Benjamin M. Nugent, Sarah J. Ryan, Michelle R. Smith, and Qiang Yang

Process Chemistry, Dow AgroSciences, 9330 Zionsville Rd., Indianapolis, Indiana 46268, United States

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.5b00417

Publication Date (Web): February 19, 2016

Copyright © 2016 American Chemical Society

*E-mail: whitekgt2@dow.com.

ACS Editors' Choice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

http://pubs.acs.org/doi/abs/10.1021/acs.oprd.5b00417

//////////

DRUG APPROVALS BY DR ANTHONY MELVIN CRASTO .....FOR BLOG HOME CLICK HERE

Join me on Linkedin

Join me on Facebook FACEBOOK

Join me on twitter     

Join me on google plus Googleplus

 amcrasto@gmail.com

KHAJURAHO INDIA Location of Khajuraho Group of Monuments in India. Location in Madhya Pradesh Khajuraho Group of Monuments - Wikipedia, the free ... en.wikipedia.org/wiki/Khajuraho_Group_of_Monuments The Khajuraho Group of Monuments are a group of Hindu and Jain temples in Madhya Pradesh, India. About 620 kilometres (385 mi) southeast of New Delhi, ... Hotel Chandela - A Taj Leisure Hotel