DR ANTHONY MELVIN CRASTO,WorldDrugTracker, helping millions, 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, nothing will not stop me except God................DR ANTHONY MELVIN CRASTO Ph.D ( ICT, Mumbai) , INDIA 25Yrs Exp. in the feld of Organic Chemistry,Working for GLENMARK GENERICS at Navi Mumbai, INDIA. Serving chemists around the world. Helping them with websites on Chemistry.Million hits on google, world acclamation from industry, academia, drug authorities for websites, blogs and educational contribution
Showing posts with label AcO[TM]Cl. Show all posts
Showing posts with label AcO[TM]Cl. Show all posts

Tuesday 1 December 2015

Ionic Liquid Ac[TM]I and AcO[TM]Cl

.

 Figure 1. 1H NMR (DMSO-d6) of AcO[TM]Cl.





 Ijms 16 07143 g002 1024


 Ijms 16 07143 g008 1024.



 Ijms 16 07143 g003 1024


 Ijms 16 07143 g004 1024


Synthesis of Ionic Liquid AcO[TM]Cl

5-(2-Acetoxyethyl)-4-methylthiazole (1.85 g, 10.0 mmol) was mixed with an excess of benzyl chloride (6.33 g, 50.0 mmol) in a round-bottom flask. The mixture was heated at 80 °C for 24 h, during which time precipitates formed. The solid was filtered off and washed with ethyl acetate. After drying under vacuum, AcO[TM]Cl was obtained as a white solid; yield: 2.51 g (81%).
1H NMR (DMSO-d6): δ 10.26 (s, 1H, thiazole ring proton), 7.25–7.45 (m, 5H, Ph), 5.77 (s, 2H, CH2Ph), 4.12 (t, J = 4.5 Hz, 2H, OCH2), 3.22 (t, J = 4.5 Hz, 2H, OCH2CH2), 2.31 (s, 3H, CH3C=O), 1.92 (s, 3H, C=C–CH3). 13C NMR (DMSO-d6): δ 169.9 (C=O), 158.6 (SCN), 142.4 (NC=C), 133.8 (SC=C), 131.1, 129.3, 129.1, 128.1 (Ph), 62.4 (OCH2), 57.0 (CH2Ph), 26.2 (OCH2CH2), 20.6 (CH3C=O), 12.4 (C=C–CH3). HRMS calculated for C15H18ClNO2S [M-H]: 310.0674; found: 310.0670.

3.3. Synthesis of Ionic Liquid Ac[TM]I

4-Methylthiazole-5-carboxylate (1.0 g, 32 mmol) was mixed with an excess of methyl iodide (2.0 mL) in a round-bottom flask, and the mixture was heated at 40 °C for 24 h. After removal of the excess methyl iodide, the partly crystalline residue was dissolved in absolute alcohol. On careful addition of diethyl ether, the product crystallized in large light yellow needles (0.85 g, 45% yield on the first crop).
1H NMR (DMSO-d6): δ 10.02 (s, 1H, thiazole ring-H), 4.09 (s, 1H, OCH3), 3.89 (s, 3H, NCH3), 2.75 (s, 3H, C=C–CH3). 13C NMR (DMSO-d6): δ 162.3 (C=O), 159.9 (SCN), 152.9 (NC=C), 125.6 (SC=C), 54.2 (O–CH3), 41.3 (NCH3), 13.1 (C=C–CH3). HRMS calculated for C7H10INO2S [M + H]+: 299.9477; found: 299.8741.



 Ijms 16 07143 g006 1024



 Ijms 16 07143 g007 1024


Int. J. Mol. Sci. 2015, 16(4), 7143-7158; doi:10.3390/ijms16047143
Article
Organocatalytic Upgrading of Furfural and 5-Hydroxymethyl Furfural to C10 and C12 Furoins with Quantitative Yield and Atom-Efficiency
Hongjun Zang and Eugene Y. X. Chen *
Department of Chemistry, Colorado State University, Fort Collins, CO 80523-1872, USA; E-Mail: zanghongjun@tjpu.edu.cn
Current address: Department of Environment and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, China.
*Author to whom correspondence should be addressed; E-Mail: eugene.chen@colostate.edu; Tel.: +1-970-491-5609; Fax: +1-970-491-1801.
Academic Editor: James H. Clark
Received: 13 February 2015 / Accepted: 26 March 2015 / Published: 30 March 2015

Abstract

: There is increasing interest in the upgrading of C5 furfural (FF) and C6 5-hydroxymethyl furfural (HMF) into C10 and C12 furoins as higher energy-density intermediates for renewable chemicals, materials, and biofuels. This work utilizes the organocatalytic approach, using the in situ generated N,S-heterocyclic carbene catalyst derived from thiazolium ionic liquids (ILs), to achieve highly efficient self-coupling reactions of FF and HMF. Specifically, variations of the thiazolium IL structure have led to the most active and efficient catalyst system of the current series, which is derived from a new thiazolium IL carrying the electron-donating acetate group at the 5-ring position. For FF coupling by this IL (0.1 mol %, 60 °C, 1 h), when combined with Et3N, furoin was obtained in >99% yield. A 97% yield of the C12 furoin was also achieved from the HMF coupling by this catalyst system (10 mol % loading, 120 °C, 3 h). On the other hand, the thiazolium IL bearing the electron-withdrawing group at the 5-ring position is the least active and efficient catalyst. The mechanistic aspects of the coupling reaction by the thiazolium catalyst system have also been examined and a mechanism has been proposed.

Keywords:
furfural; 5-hydroxymethyl furfural (HMF); umpolung coupling; organocatalysis; N-heterocyclic carbene; ionic liquid; biomass; biorefining
 http://www.mdpi.com/1422-0067/16/4/7143/htm




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


Join me on Linkedin

View Anthony Melvin Crasto Ph.D's profile on LinkedIn

Join me on Facebook FACEBOOK
Join me on twitterFollow amcrasto on Twitter     
Join me on google plus Googleplus

 amcrasto@gmail.com

//////////