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Summary

Abstract

Introduction

Protocol

Representative Results

Discussion

Acknowledgements

Materials

References

Chemistry

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

Published: July 23rd, 2016

DOI:

10.3791/54054

1Autonomous Metropolitan University-Azcapotzalco, 2Institute of Catalysis and Petroleum Chemistry, ICP-CSIC, 3Department of Chemistry, Autonomous Metropolitan University-Iztapalapa, 4Department of Chemistry, Center of Investigation and Superior Studies (IPN), 5Research Institute of Material, National Autonomous University of Mexico

The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained.

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.

The use of porous coordination polymers (PCPs) as heterogeneous catalysts1-4 is a relatively new research field. Due to very interesting properties that PCPs show, e.g., porous regularity, high surface area and metal access, they can offer new alternatives for heterogeneous catalysts5-6. The generation of catalytically active PCPs has been the main focus of many research groups7-10. A porous coordination polymer is constituted by metal ions and organic linkers and thus, the catalytic activity of these materials is provided by any of these parts. Some PCPs contain unsaturated (active) metals that can catalyze a chemical reactio....

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CAUTION: The chemicals used in this catalytic procedure are relatively low in toxicity and non-carcinogenic. Please use all appropriate safety precautions when performing this experimental procedure such as safety glasses, gloves, lab coat, full length pants and closed-toe shoes. One part of the following procedures involves standard air-free handling techniques.

1. Activation of the Catalyst (HKUST-1)

  1. Crystallinity Characterization of the Catalyst
    Note: HKUST-1 is a commercially available porou.......

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Three representative samples of HKUST-1 were analyzed by infrared spectroscopy: non-activated, activated at 100 °C for 1 hr in an oven (exposed to air), and activated under vacuum (10-2 bar) at 100 °C for 1 hr. Thus, Fourier transform infrared (FTIR) spectra were recorded using a spectrometer with a single reflection diamond ATR accessory (Figure 1). For all spectra, 64 scans in the 4,000 to 400 cm-1 range were recorded with a spectral reso.......

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The fundamental step for the catalytic conversion of trans-ferulic acid to vanillin was the activation of the catalyst (HKUST-1). If the catalyst is not activated in situ (under vacuum and at 100 °C), only partial conversion of trans-ferulic acid to vanillin was observed44. In other words, the accessibility to open metal sites is crucial for the catalytic cycle44, and this can be achieved by the elimination of coordinated water to the Cu(II) metal sites within the por.......

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The authors thank Dr. A. Tejeda-Cruz (X-ray; IIM-UNAM). R.Y. thanks CINVESTAV, Mexico for technical support. M.S.S acknowledges the financial support by Spanish Government, MINECO (MAT2012-31127). I.A.I thanks CONACyT (212318) and PAPIIT UNAM (IN100415), Mexico for financial support. E.G-Z. thanks CONACyT (156801 and 236879), Mexico for financial support. Thanks to U. Winnberg (ITAM and ITESM) for scientific discussions.

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Name Company Catalog Number Comments
HKUST-1 Sigma-Aldrich MFCD10567003
Ferulic Acid (trans-4-Hydroxy-3-methoxycinnamic acid) Sigma-Aldrich 537-98-4
Ethanol Sigma-Aldrich 64-17-5
Hydrogen peroxide solution Sigma-Aldrich  7722-84-1
Acetonitrile Sigma-Aldrich 75-05-8
Ethyl acetate Sigma-Aldrich 141-78-6
Ammonium chloride Sigma-Aldrich 12125-02-9
Sodium sulfate anhydrous Sigma-Aldrich 7757-82-6
Ethyl acetate Sigma-Aldrich 141-78-6
n-Hexane Sigma-Aldrich 110-54-3
Silica Gel Sigma-Aldrich 112926-00-8  Size 70/230
250 mL two-neck round-bottom flask Sigma-Aldrich Z516872-1EA 250 mL capacity
Magnetic stirring bar Bel-Art products 371100002 Teflon, octagon
Condenser Cole-Parmer JZ-34706-00 200 mm Jacket length
Vacuum pump (Approx. 10X-2 bar) Cole-Parmer JZ-78162-00 Vacuum/Pressure Diaphragm Pump
Stopcock Cole-Parmer EW-30600-00 with a male luer slip
Hose Cole-Parmer JZ-06602-04 16.0 mm ID and 23.2 mm ED
Rubber septums Cole-Parmer JZ-08918-34 Silicone with PTFE coating
Hot plate Cole-Parmer JZ-04660-15 10.2 cm x 10.2 cm, 5 to 540 °C
Sand bath  Cole-Parmer GH-01184-00 Fluidized Sand Bath SBS-4, 50 to 600 °C
N2 gas INFRA Cod. 103 Cylinder 9m ³
Ballons (filled with N2 gas) Sigma-Aldrich Z154989-100EA Thick-wall, natural latex rubber
Syringes with removable needles Sigma-Aldrich Z116912-100EA 10 mL capacity
Filter paper Cole-Parmer JZ-81050-24 Grade No. 235 qualitative filter paper (90 mm diameter disc)
Buchner funnel Cole-Parmer JZ-17815-04 320 mL capacity which accept standard paper filter sizes 
Buchner flask Cole-Parmer JZ-34557-02 250 mL capacity
Rotary Evaporator Cole-Parmer JZ-28710-02
Beakers Cole-Parmer JZ-34502-(02,04,05) Pyrex Brand 1000 Griffin; 20, 50 and 100 mL
Separation funnel  Cole-Parmer JZ-34505-44 Capacity for 125 mL with steam lenght of 60 mm
Glass column for chromatography Cole-Parmer JZ-34695-42 Column with fritted disk, 10.5 mm ID x 250 mm L
PXRD diffractometer Bruker AXS D8 Advance XRD
FTIR spectrophotometer Thermo scientific FT-IR (JZ-83008-02); ATR (JZ-83008-26) Nicolet iS5 FT-IR Spectrometer, with KBr Windows and iD5 Diamond ATR

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