CO2-Catalysed aldol condensation of 5-hydroxymethylfurfural and acetone to a jet fuel precursor

CO2-Catalysed aldol condensation of 5-hydroxymethylfurfural and acetone to a jet fuel precursor

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC01697A, Communication

Roland Lee, Jesse R. Vanderveen, Pascale Champagne, Philip G. Jessop
CO₂ can act as a catalyst for the production of bio-jet fuel precursors through aldol condensation.

Roland Lee,^a   Jesse R. Vanderveen,^a   Pascale Champagne^b and  Philip G. Jessop*^a  

 *Corresponding authors

^aDepartment of Chemistry, Queen’s University, Kingston, Canada K7L 3N6
E-mail: Philip.jessop@queensu.ca

^bDepartment of Civil Engineering, Queen’s University, Kingston, Canada K7L 3N6

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC01697A, http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC01697A?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

CO₂ can act as a catalyst for the production of bio-jet fuel precursors through aldol condensation. CO₂-Catalysed aldol condensation of HMF with acetone gives a >95% yield of [4-(5-hydroxymethyl-2-furyl)-3-butenone] mono-aldol condensate, while direct conversion of glucose to the same mono-aldol condensate gave a yield of 11%

Method Single step dehydration, aldol condensation, and hydrogenation was carried out in a Parr 31 mL high pressure vessel (T316SS, Parr no. N4742, modified to 31 mL). Glucose/5-HMF, hydrogenation catalyst (Pt (nominally 50 %), Ru (nominally 25 %) on high surface area advanced carbon support supplied by Alfa Aesar (stock# 12100) and reaction solvents were added to the Parr vessel equipped with a stir bar. The vessel was then closed and heated in an oil bath to the required temperature and allowed to equilibrate for 30 min. Following equilibration, the reactor was pressurized with CO2 and H2 to operating conditions. Following reaction (both for conversion of 5-HMF to aldol condensation product or direct conversion from glucose) and dilution, the samples were analyzed with the use of GC-MS (Perkin Elmer Clarus 680 gas chromatograph (GC)), using an Elite-5MS column (30 m, 250 µm i.d., 0.25 µm film of 5% diphenyl 95% dimethyl polysiloxane). Initially the temperature was held at 30 °C for 0 min, followed by a ramp to 125 °C at a rate of 2.5 °C /min held for 1 min, ramp to 260 °C at a rate of 20 °C /min held for 1 min and, finally, ramp to 300 °C at a rate of 20 °C /min held for 3 min. The injector temperature was held at 250 °C and the detector at 200 °C for the duration of the analysis. Carrier gas (helium) flow rate was maintained at 1 mL/min. Aldol condensation products were independently prepared by a literature method17 and utilized for calibration and determination of retention time. Chromatograms and data were collected precisely with the use of Perkin Elmer TurboMass, version 5.4.2.1617 chromatography software.

Scheme 1 Proposed conversion of cellulose to biomass derived jet fuel.

///////////CO₂-Catalysed,  aldol condensation, -hydroxymethylfurfural, jet fuel precursor

Visible-light induced oxidative Csp3-H activation of methyl aromatics to methyl esters

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC01880G, Communication

Lingling Zhang, Hong Yi, Jue Wang, Aiwen Lei
A mild and catalytic oxidative Csp³-H activation of methyl aromatics using O₂via photocatalysis has been achieved. A lot of methyl aromatics can be tolerated, providing a route for aromatic methyl carboxylates. In addition, this protocol can be performed on a gram scale

Visible-light induced oxidative Csp3-H activation of methyl aromatics to methyl esters

Lingling Zhang,^a   Hong Yi,^a   Jue Wang^a and   Aiwen Lei*^ab  

*Corresponding authors

^aCollege of Chemistry and Molecular Sciences, the Institute for Advanced Studies, Wuhan University, Wuhan, P. R. China
E-mail: aiwenlei@whu.edu.cn

^bNational Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang 330022, P. R. China

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC01880G. http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC01880G?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Direct functionalization of readily available hydrocarbons under mild conditions fulfills the requirements of green and sustainable chemistry. In this work, a mild and green catalytic oxidative Csp³–H activation of methyl aromatics using O₂ via photocatalysis has been achieved. A lot of methyl aromatics can be tolerated, providing a green route for aromatic methyl carboxylates. In addition, this protocol can be performed on a gram scale.

Methyl 4-methylbenzoate (2a): [1] 32.9 mg (yield: 73%, light yellow oil). 1H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 8.1 Hz, 2H), 7.06 (d, J = 8.0 Hz, 2H), 3.73 (s, 3H), 2.22 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 167.0, 143.5, 129.6, 129.0, 127.4, 51.8, 21.5.

Liu, H.; Chen, G.; Jiang, H.; Li, Y.; Luque, R., ChemSusChem. 2012, 5 , 1892-1896.

///////Visible-light,  induced oxidative,  Csp3-H activation,  methyl aromatics, methyl esters

KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki-Miyaura cross-coupling

KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki-Miyaura cross-coupling

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC02012G, Paper

Prashant Gautam, Mahak Dhiman, Vivek Polshettiwar, Bhalchandra M. Bhanage
This work reports a cost-effective and sustainable protocol for the carbonylative Suzuki-Miyaura cross-coupling reaction catalyzed by palladium nanoparticles (Pd NPs) supported on fibrous nanosilica (KCC-1) with very high turnover number.

http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC02012G?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

This work reports a cost-effective and sustainable protocol for the carbonylative Suzuki–Miyaura cross-coupling reaction catalyzed by palladium nanoparticles (Pd NPs) supported on fibrous nanosilica (KCC-1). Under mild reaction conditions, the KCC-1-PEI/Pd catalytic system showed a turnover number (TON) 28-times and a turnover frequency (TOF) 51-times higher than the best supported Pd catalyst reported in the literature for the carbonylative cross-coupling between 4-iodoanisole and phenylboronic acid, as a test reaction. Also, the catalyst could be recycled up to ten times with a marginal loss in activity after the eighth cycle. The high activity of the catalyst can be attributed to the fibrous nature of the KCC-1 support and PEI functionalization provided the enhanced stability.

(4-methoxyphenyl)(phenyl)methanone (3b) 59.3 mg, yield 56%

1H NMR (500 MHz, CDCl3): δ 7.86 (d, J = 8.6 Hz, 2H), 7.78 (d, J = 7.6 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.6 Hz, 2H), 6.99 (d, J = 8.6 Hz, 2H), 3.92 (s, 3H).

13C{1H}NMR (125 MHz, CDCl3): δ 195.4, 163.1, 138.2, 132.4, 131.8, 130.0, 129.6, 128.1, 113.4, 55.4.

GCMS (EI, 70 eV): m/z (%): 212 (40), 135 (100), 105 (14), 77 (36).

 

 

 

Prashant Gautam,^a   Mahak Dhiman,^b   Vivek Polshettiwar*^b and  Bhalchandra M. Bhanage*^a  

*Corresponding authors

^aDepartment of Chemistry, Institute of Chemical Technology, N.P. Marg, Matunga-400019, Mumbai, India
E-mail: bm.bhanage@ictmumbai.edu.in,bm.bhanage@gmail.com

^bNanocatalysis Laboratories (NanoCat), Department of Chemical Sciences, Tata Institute of Fundamental Research (TIFR), Homi Bhabha Road, Colaba, Mumbai, India
E-mail: vivekpol@tifr.res.in

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC02012G

Prashant Gautam

Bhalchandra M. Bhanage

\\\\\\\\\\KCC-1 supported,  palladium nanoparticles, sustainable nanocatalyst, carbonylative Suzuki-Miyaura cross-coupling, Prashant Gautam, Mahak Dhiman, Vivek Polshettiwar, Bhalchandra M. Bhanage