Name: hkust-1 as a heterogeneous catalyst for the synthesis of vanillin
Uploaded: 2016-07-23T14:00:00
Description: Watch this Scientific Journal Video about HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin at JoVE.com

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.

注意：この触媒の手順で使用される化学物質は、毒性および非発癌性が比較的低いです。このような安全眼鏡、手袋、白衣、完全長ズボンとクローズドつま先の靴のように、この実験手順を実行するとき、すべての適切な安全対策を使用してください。次の手順の一部は、標準的な空気のないハンドリング技術を必要とします。 触媒の1.アクティベーション（HKUST-1） <ol><li>触媒の結晶...

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Biotechnol. 44 (3), 335-353 (2006).</li><li>Yepez, R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Catalytic+activity+of+HKUST-1+in+the+oxidation+of+trans-ferulic+acid+to+vanillin.">Catalytic activity of HKUST-1 in the oxidation of trans-ferulic acid to vanillin.</a> New. J. Chem. 39 (7), 5112-5115 (2015).</li></ol>

バニリンへのトランス -ferulic酸の触媒変換のための基本的なステップは、触媒（HKUST-1）の活性化でした。触媒は、（真空下で100℃で）、その場で活性化されていない場合、バニリンのトランス -ferulic酸の唯一の部分的変換は44を観察しました。換言すれば、金属部位を開くためのアクセス可能性は、触媒サイクル44のために重要であり、これは、多孔性配?...

不均一系触媒1-4のような多孔性配位高分子（のPCP）の使用は比較的新しい研究分野です。 PCPが示す非常に興味深い特性、 例えば、多孔性の規則性、高表面積と金属のアクセスのために、彼らは不均一系触媒5-6のための新たな選択肢を提供することができます。触媒活性のPCPの生成は、多くの研究グループ7-10の主な焦点となっています。多孔性配位高分子は、金属イオン、有機リンカーで構成され、したがって、これらの材料の触媒活性は、これらの部品のいずれかによって提供されます。いくつかのPCPは、化学反応11を触媒することができる不飽和（アクティブ）な金属が含まれています。しかし、配位高分子内の不飽和金属部位（オープン金属部位）の生成は簡単な作業ではありません、それはに要約することができる合成挑戦表す：不安定なリガンド7-11の除去により空い協調の生成（i）を 、（ii）の有機金属配位子（あらかじめ合成）8,12-13を組み込むことにより、バイメタルのPCPの生成を、 （iii）の金属イオンのPCPの細孔内9,14-15または有機配位子10、16-17の合成後の変化。方法（i）は 、従って最も簡単であるので、最も頻繁に使用されます。典型的に、開いた金属部位の生成はH 2 18〜19の方へのPCPの親和性を高めるために使用されているだけでなく、活性の不均一触媒を20〜27を設計します。良好な触媒特性を達成するために、のPCPは、さらに開いた金属部位のアクセシビリティに、反応条件、熱安定性および化学的安定性が比較的高い触媒実験後の結晶化度の保持率を示す必要があります。 HKUST-1銅（Cu 3（BTC）2（H 2 O）3、BTC = 1,3,5-ベンゼントリカルボキシレート）7カルボキシレート配位子と水に配位されたCu（II）陽イオンで構成よく調べ多孔性配位高分子、。興味深いことに、これらの水分子は、（加熱により）除去することができ、これはハードルイス酸特性11を示す銅イオンの周りの正方形平面調整を提供します。 Bordigaと 共同研究者28は、これらの H 2 O分子の脱離は、結晶性（規則性の保持）と金属イオンの酸化状態（銅（II））の影響を受けなかった影響を及ぼさなかったことを示しました。触媒としてHKUST-1の使用は広範囲に芳香族分子34の過酸化水素による酸化（本研究のために非常に関連する）29-33を調査し、特にされています。 バニラは、化粧品、医薬品及び食品産業において最も広く使用されている香味剤の一つです。これは、蘭ヴァニラプラニフォリア、バニの硬化豆から抽出されますLLAのtahitiensisとバニラポンポン 。それはチョコレートフレーバー35-37が改善するので、マヤやアステカ文明（プレコロンビア人）は、最初の香味剤としてバニラの莫大な可能性を実現しました。バニラは、まず1858年38で分離された、それはバニリンの化学構造が最終的に決定されたことを1874年39までではなかったです。 （蘭ヴァニラプラニフォリア、バニラtahitiensisとバニラのポンポンから）バニリンの天然抽出は世界生産の1％のみを表しており、このプロセスは高価であり、40は非常に長いため、バニリンの残りの部分は、40合成されます。これらのプロセスは、強力な酸化剤および毒性の溶媒41〜43を使用するので、多くの生物工学的手法等リグニン、フェノールスチルベン、イソオイゲノール、オイゲノール、guaicolからバニリンの合成に用いることができるが、これらの方法は、環境に害を与えるという欠点を有します。ここで、我々はrを触媒としてHKUST-1を使用して、トランス -ferulic酸の酸化によってバニリンの製造のための合成戦略をEPORT。

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>HKUST-1</td>
			<td>Sigma-Aldrich</td>
			<td>MFCD10567003</td>
			<td></td>
		</tr>
		<tr>
			<td>Ferulic Acid (trans-4-Hydroxy-3-methoxycinnamic acid)</td>
			<td>Sigma-Aldrich</td>
			<td>537-98-4</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethanol</td>
			<td>Sigma-Aldrich</td>
			<td>64-17-5</td>
			<td></td>
		</tr>
		<tr>
			<td>Hydrogen peroxide solution</td>
			<td>Sigma-Aldrich</td>
			<td>&#160;7722-84-1</td>
			<td></td>
		</tr>
		<tr>
			<td>Acetonitrile</td>
			<td>Sigma-Aldrich</td>
			<td>75-05-8</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethyl acetate</td>
			<td>Sigma-Aldrich</td>
			<td>141-78-6</td>
			<td></td>
		</tr>
		<tr>
			<td>Ammonium chloride</td>
			<td>Sigma-Aldrich</td>
			<td>12125-02-9</td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium sulfate anhydrous</td>
			<td>Sigma-Aldrich</td>
			<td>7757-82-6</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethyl acetate</td>
			<td>Sigma-Aldrich</td>
			<td>141-78-6</td>
			<td></td>
		</tr>
		<tr>
			<td>n-Hexane</td>
			<td>Sigma-Aldrich</td>
			<td>110-54-3</td>
			<td></td>
		</tr>
		<tr>
			<td>Silica Gel</td>
			<td>Sigma-Aldrich</td>
			<td>112926-00-8</td>
			<td>&#160;Size 70/230</td>
		</tr>
		<tr>
			<td>250 mL two-neck round-bottom flask</td>
			<td>Sigma-Aldrich</td>
			<td>Z516872-1EA</td>
			<td>250 mL capacity</td>
		</tr>
		<tr>
			<td>Magnetic stirring bar</td>
			<td>Bel-Art products</td>
			<td>371100002</td>
			<td>Teflon, octagon</td>
		</tr>
		<tr>
			<td>Condenser</td>
			<td>Cole-Parmer</td>
			<td>JZ-34706-00</td>
			<td>200 mm Jacket length</td>
		</tr>
		<tr>
			<td>Vacuum pump (Approx. 10X-2 bar)</td>
			<td>Cole-Parmer</td>
			<td>JZ-78162-00</td>
			<td>Vacuum/Pressure Diaphragm Pump</td>
		</tr>
		<tr>
			<td>Stopcock</td>
			<td>Cole-Parmer</td>
			<td>EW-30600-00</td>
			<td>with a male luer slip</td>
		</tr>
		<tr>
			<td>Hose</td>
			<td>Cole-Parmer</td>
			<td>JZ-06602-04</td>
			<td>16.0 mm ID and 23.2 mm ED</td>
		</tr>
		<tr>
			<td>Rubber septums</td>
			<td>Cole-Parmer</td>
			<td>JZ-08918-34</td>
			<td>Silicone with PTFE coating</td>
		</tr>
		<tr>
			<td>Hot plate</td>
			<td>Cole-Parmer</td>
			<td>JZ-04660-15</td>
			<td>10.2 cm x 10.2 cm, 5 to 540 &#176;C</td>
		</tr>
		<tr>
			<td>Sand bath&#160;</td>
			<td>Cole-Parmer</td>
			<td>GH-01184-00</td>
			<td>Fluidized Sand Bath SBS-4, 50 to 600 &#176;C</td>
		</tr>
		<tr>
			<td>N2 gas</td>
			<td>INFRA</td>
			<td>Cod. 103</td>
			<td>Cylinder 9m &#179;</td>
		</tr>
		<tr>
			<td>Ballons (filled with N2 gas)</td>
			<td>Sigma-Aldrich</td>
			<td>Z154989-100EA</td>
			<td>Thick-wall, natural latex rubber</td>
		</tr>
		<tr>
			<td>Syringes with removable needles</td>
			<td>Sigma-Aldrich</td>
			<td>Z116912-100EA</td>
			<td>10 mL capacity</td>
		</tr>
		<tr>
			<td>Filter paper</td>
			<td>Cole-Parmer</td>
			<td>JZ-81050-24</td>
			<td>Grade No. 235 qualitative filter paper (90 mm diameter disc)</td>
		</tr>
		<tr>
			<td>Buchner funnel</td>
			<td>Cole-Parmer</td>
			<td>JZ-17815-04</td>
			<td>320 mL capacity which accept standard paper filter sizes&#160;</td>
		</tr>
		<tr>
			<td>Buchner flask</td>
			<td>Cole-Parmer</td>
			<td>JZ-34557-02</td>
			<td>250 mL capacity</td>
		</tr>
		<tr>
			<td>Rotary Evaporator</td>
			<td>Cole-Parmer</td>
			<td>JZ-28710-02</td>
			<td></td>
		</tr>
		<tr>
			<td>Beakers</td>
			<td>Cole-Parmer</td>
			<td>JZ-34502-(02,04,05)</td>
			<td>Pyrex Brand 1000 Griffin; 20, 50 and 100 mL</td>
		</tr>
		<tr>
			<td>Separation funnel&#160;</td>
			<td>Cole-Parmer</td>
			<td>JZ-34505-44</td>
			<td>Capacity for 125 mL with steam lenght of 60 mm</td>
		</tr>
		<tr>
			<td>Glass column for chromatography</td>
			<td>Cole-Parmer</td>
			<td>JZ-34695-42</td>
			<td>Column with fritted disk, 10.5 mm ID x 250 mm L</td>
		</tr>
		<tr>
			<td>PXRD diffractometer</td>
			<td>Bruker</td>
			<td></td>
			<td>AXS D8 Advance XRD</td>
		</tr>
		<tr>
			<td>FTIR spectrophotometer</td>
			<td>Thermo scientific</td>
			<td>FT-IR (JZ-83008-02); ATR (JZ-83008-26)</td>
			<td>Nicolet iS5 FT-IR Spectrometer, with KBr Windows and iD5 Diamond ATR</td>
		</tr>
	</tbody>
</table>

hkust-1 as a heterogeneous catalyst for the synthesis of vanillin

バニリン（4-hydoxy -3-メトキシベンズアルデヒド）は、バニラ豆の抽出物の主成分です。自然なバニラの香りは、バニリンに加えて、約200の異なる着臭剤化合物の混合物です。 （蘭ヴァニラプラニフォリア、バニラtahitiensisとバニラのポンポンから）バニリンの天然抽出は世界生産の1％のみを表しており、このプロセスは高価であり、非常に長いため、バニリンの生産の残りの部分が合成されます。多くの生物工学的ア ​​プローチは、これらのプロセスは、強力な酸化剤と有毒な溶媒を使用するので、環境に害を与えるという欠点を有する等リグニン、フェノールスチルベン、イソオイゲノール、オイゲノール、guaicolからバニリンの合成に使用することができます。このように、バニリンの生産に環境に優しい代替案は、現在調査中で、このように非常に望ましいものであると。多孔性配位高分子（のPCP）はREC高結晶性物質の新しいクラスでありますまったく別触媒反応のために使用されています。 HKUST-1銅（Cu 3（BTC）2（H 2 O）3、BTC = 1,3,5-ベンゼントリカルボキシレート）は、広く不均一触媒として研究されている、非常によく知られたPCPです。ここでは、触媒としてHKUST-1を使用して、トランス -ferulic酸の酸化によるバニリンの製造のための合成戦略を報告しています。

HKUST-1の3つの代表的なサンプルは、赤外分光法によって分析した：非活性化、（空気にさらさ）オーブン中で1時間100℃で活性化され、1 100℃で真空（10 -2バール）下で活性化時間。したがって、フーリエ変換赤外（FTIR）スペクトルは、単反射ダイヤモンドATRアクセサリー（ 図1）を有する分光計を用いて記録した変換します。すべてのスペクトル?...

Watch this Scientific Journal Video about HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin at JoVE.com

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

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.

HKUST-1バニリンの合成のための不均一触媒として、

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately ...

The overall goal of this methodology is the conversion of trans ferulic acid to vanillin by heterogeneous catalysis using the porous coordination polymer HKUST-1. The essential step in the catalytic process is the generation of unsaturated metal sites in HKUST-1. These methods can help us answer key questions in the heterogeneous catalysis field, such as in the production of vanillin, which is one of the most widely employed flavoring agents in the world.The main advantage of this technique is that we provide an experimental protocol to catalytically convert ferulic acid to vanillin under mild oxidation conditions. The implications of this technique extend toward the use of porous coordination polymers as catalysts. Generally, individuals new to this method will struggle, because activation of the HKUST-1 material is fundamental.Demonstrating the procedure will be Rebeca Yepez, a graduate student from my laboratory. To characterize the crystallinity of the catalyst, collect the powder x-ray diffraction pattern of a 0.1 gram sample of HKUST-1, as described in the text protocol. Record a powder x-ray diffraction pattern from five degrees to 60 degrees in 0.02 degree steps, and one second counting time.Then, perform dissolvation of HKUST-1 by first weighing 0.05 grams of the catalyst. Next, prepare the activation system by clamping a 250 milliliter two neck round bottom flask to a stand and inserting a magnetic stirring bar into the round bottom flask. Attach a condenser to the round bottom flask.Use some vacuum grease or Teflon tape between the joints of the flask and condenser to generate a perfect seal. Connect the condenser from the top to a vacuum pump. Make sure that the vacuum generated by the pump is approximately 0.1 bar.Place the catalyst inside the 250 milliliter two neck round bottom flask. Insert a rubber septum in the second neck of the round bottom flask, and make sure that it seals properly. Carefully place the activation system into a sand bath.Start the vacuum pump and carefully turn the stopcock until it is fully opened. With a hot plate, heat the activation system up to 100 degrees Celsius for one hour. Stir at the lowest speed, the hot plate to homogeneously distribute the catalyst at the bottom of the round bottom flask.When the catalyst is activated, a color change must be clearly observed. This is an indication of the removal of coordinated water molecules, and therefore the generation of coordinately unsaturated copper to metal sites within the catalyst. A color change from turquoise to dark blue upon activation is observed.Turn off the heat after one hour of heating and let the activation system cool to room temperature. Once the activation system is cooled down to room temperature, turn the stopcock off, and turn the pump off. Connect a balloon filled with nitrogen though the septum to the two neck round bottom flask, and wait a few seconds to reach the equilibrium pressure.After the activation of the catalyst, leave it under an inert atmosphere, since the access to the uncoordinated metal sites is the key to obtaining an active catalyst. Remove the balloon filled with nitrogen when the equilibrium pressure has been achieved. De-gas approximately 70 milliliters of ethanol by bubbling nitrogen for five minutes.To prepare the catalytic reaction, add 10 milliliters of de-gassed ethanol to the two neck round bottom flask and gently stir the suspension on a hot plate. Then, add five milliliters of hydrogen peroxide followed by 25 milliliters of acetonitrile to the suspension. Weigh 0.5 grams of ferulic acid and dissolve it in 20 milliliters of de-gassed ethanol in a beaker.Add the dissolved ferulic acid to the suspension, then wash the beaker with 20 milliliters of de-gassed ethanol and add it to the suspension. For oxidation of trans ferulic acid to vanillin, first unplug the hose that connects the condenser to the vacuum pump. Turn on the tap water, or preferably, the water pump that goes though the condenser.Heat the suspension up to 100 degrees Celsius and reflux for one hour. After turning off the heat and stirring, carefully lift the two neck round bottom flask attached to the condenser and let it cool to room temperature. Next, filter off the reaction mixture using a Buchner funnel and flask.Recover the catalyst and wash it with 200 milliliters of ethyl acetate. Concentrate the combined organic phases under vacuum with a rotary evaporator and re-dissolve it with 100 milliliters of ethyl acetate. Wash the organic phases in a separation funnel with a 30 milliliter saturated solution of ammonium chloride.Then, recover the organic phases and mix them with 30 grams of anhydrous sodium sulfate. After letting the suspension stand for 15 minutes, filter the suspension off, and recover the filtrate. Then, concentrate the filtrate to approximately 20 milliliters under vacuum with a rotary evaporator.Purify the residue by flash column chromatography. The stationary phase is silica gel, and the mobile phase is a solvent mixture of ethyl acetate and hexane. Pack the glass column for chromatography with a silica gel.Then, saturate the column with the ethyl acetate hexane solvent mixture. Carefully pour the concentrated filtrate on top of the glass column. Slowly add the solvent mixture to the glass column and collect all of the fractions until 1, 200 milliliters are collected.Concentrate the 1, 200 milliliters of the organic fractions with a rotary evaporator until dry. Recover the final solid powder that is the purified vanillin. Shown here are fourier transform infrared spectra of the HKUST-1 catalyst at 25 degrees Celsius.The spectrum of the non-activated catalyst is shown in green. The spectrum of the activated catalyst in a conventional oven is shown in purple, and the spectrum of the activated catalyst under vacuum is shown in orange. Shown here is a proton NMR spectra of vanillin after column chromatography purification on silica gel when the catalyst was activated under vacuum and 100 degrees Celsius for one hour.Once mastered, this technique can be done in four hours, if it is performed properly. Though this method can provide insight into the mechanism for the oxidation of trans ferulic acid, it can also be applied to other systems, such as oxidation of other alpha beta unsaturated carboxylic acid. While attempting this procedure, it's important to remember to emphasize on the correct purification of vanillin by column chromatography.Following this procedure, other methods like the oxidation of other alpha beta unsaturated carboxylic acid can be performed in order to answer additional questions, like oxidation mechanisms. After its development, this technique paved way for researchers in the field of porous coordination polymers to explore these materials as heterogeneous catalyst to synthesize molecules of high chemical relevance. After watching this video, you should have a good understanding of how to carry out the oxidation of ferulic acid to vanillin.Don't forget that working with a high volatility solvents under reflexive conditions can be extremely hazardous, and precautions such as wearing a lab coat, safety glasses, and working in a fume hood, should always be taken while performing this procedure.

Research

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