CN1060466C - 一种还原－酯化合成羧酸酯的方法 - Google Patents
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Abstract
本发明属于还原-酯化制备羧酸酯的方法。
将现有的酯化反应和还原反应合二为一，采用特殊制备的骨架镍催化剂，制备步骤是将镍铝合金用氢氧化钠溶液消化后，再用金属卤化物进行处理，所制得的催化剂与不饱和酸、醇一起反应，简化了反应步骤，产品总得不低于70%，反应转化率不低于80%。
Description
本发明是合成羧酸酯的方法。
羧酸与醇在酸性或碱性条件下可以进行酯化反应生成各种羧酸酯。这些酯类化合物有着广泛的用途，例如在香料行业用作调配各种香型的香精，在材料行业用作高分子助剂，在化妆品、食品行业用作表面活性剂等。在酯化方法中不论使用酸性催化剂，如无机酸、超强酸或阳离子交换树脂等，还是碱性催化剂，如无机碱、阴离子交换树脂等，都只是单纯的酯化反应发生。在实际应用中，有些酯类化合物要经过多步反应才能得到，这样的过程必然造成总得率不高。
羧酸与醇在酸性或碱性条件下可以进行酯化反应生成各种羧酸酯，如苯甲酸与对甲氧基苯酚在H3BO3／H2SO4存在下的酯化反应(Lowrance，W．W．，TetrahedronLett．，1971，3453)。为减少反应步骤，降低成本，对于两步反应合并成一步反应，一般较常见的是伯醇的氧化—酯化反应。伯醇可被多种氧化剂氧化成酸，当有过量醇存在时，则生成酯。常用的氧化剂有重铬酸钠—硫酸，次氯酸叔丁酯等。例如在吡啶存在下，次氯酸叔丁酯将3—甲基丁醇首先氧化成酸，继而与另一分子醇脱水酯化以良好的收率生成酯(Grob，C．A．And Schmid，H．J．，Helv．Chim．Acta．，1953，36，1763)。又如，活性二氧化锰在氰化钠及醇存在下，可使丙烯醇氧化成酯(E．J．Corey，N．W．Gilman，B．E．Ganem，J．Am．Chem．Soc．，1968，90，5616)。
本发明提供一种更简便的一步合成羧酸酯的方法。
本发明提供的合成羧酸酯的方法是采用易于制备的经过特殊处理的骨架镍催化剂，使用固定床反应釜，将通常的还原反应和酯化反应连续操作。实施方案如下：
1．催化剂的制备和处理(修饰)
将镍铝合金(镍铝含量比为1∶1)在温度90～95℃的条件下，加入10％重量浓度的氢氧化钠溶液中，消化(即氢氧化钠与镍铝合金进行反应)1小时，然后用清水和无水乙醇洗涤后，将制得的催化剂放入重量浓度为10％的金属卤化物溶液中浸泡24小时，进行催化剂的处理或修饰，得到发明所适用的骨架镍催化剂。
2．还原—酯化反应
将不饱和酸、醇和上述实施方案1中得到的催化剂加入反应器中，在60～160℃下搅拌，在氢气存在下进行反应。
本发明提供的将不饱和酸或不饱和醇的还原反应与酯化反应合二为一的还原—酯化方法制备羧酸酯类，缩短了反应步骤，而产品总得率不低于70％，反应转化率不低于80％。
实例一
肉桂酸与乙醇反应制备3—苯丙酸乙酯
在反应釜中依次加入实施方案(1)所述的催化剂5克，肉桂酸30克和无水乙醇100毫升。加料后，用氢气置换反应釜内的空气3次。将釜内压力调至45～48公斤／平方厘米，温度设置为80℃。加热，控制釜内最高压力不超过60公斤／平方厘米，最高温度不超过100℃，同时将压力设置调节为60公斤／平方厘米，温度设置调节为100℃。用气相色谱检测反应进行情况。反应完成后，降至室温。放出反应液，集中蒸馏。釜内剩余催化剂留至下一釜使用。
实例二
肉桂酸与乙醇反应制备3—苯丙酸乙酯
在实例一刚放出反应液后的反应釜中，补充4克催化剂，加入肉桂酸30克和无水乙醇100毫升。重复实例一的其他操作。将集中的反应液蒸馏分离出过量乙醇后，减压条件下精密蒸馏得到3—苯丙酸乙酯，沸点128～130℃／15mmHg，按肉桂酸计算，得率70％。
实例三
丁酸与烯丙醇反应制备丁酸丙酯
在反应釜中依次加入催化剂5克，丁酸30克和烯丙醇100毫升。加料后，用氢气置换反应釜内的空气3次。将釜内压力调至45～48公斤／平方厘米，温度设置为80℃。加热，控制釜内最高压力不超过60公斤／平方厘米，最高温度不超过100℃，同时将压力设置调节为60公斤／平方厘米，温度设置调节为100℃。用气相色谱检测反应进行情况。反应完成后，降至室温。放出反应液，集中蒸馏。
Claims (1)
1．一种还原—酯化合成酯的方法，其特征在于，还原和酯化合二为一，采用重新制备和处理的骨架镍催化剂，该方法步骤包括：
1)催化剂制备和修饰
将镍铝含量比为1∶1的镍铝合金在温度90～95℃的条件下，加入10％重量浓度的氢氧化钠溶液中，消化反应一小时，然后用清水和无水乙醇洗涤后，将制得的产物放入重量浓度为10％的金属卤化物溶液中浸泡24小时，进行催化剂的修饰处理；
2)还原—酯化反应：
将上述1)中所得到的经修饰的骨架镍催化剂和不饱和酸及醇类，60～160℃在氢气存在下反应。
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| CN103084209B (zh) * | 2011-10-27 | 2014-12-10 | 中国科学院大连化学物理研究所 | 一种镍基微孔材料在催化酯化反应中的应用 |
| WO2013060173A1 (zh) * | 2011-10-27 | 2013-05-02 | 中国科学院大连化学物理研究所 | 一种镍基微孔材料及其制备和应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0114704A2 (en) * | 1983-01-20 | 1984-08-01 | Unilever N.V. | Nickel-based catalyst, its preparation and its application |
| JPH03249946A (ja) * | 1990-02-28 | 1991-11-07 | Nard Inst Ltd | ラネーＮｉ系触媒の製法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0114704A2 (en) * | 1983-01-20 | 1984-08-01 | Unilever N.V. | Nickel-based catalyst, its preparation and its application |
| JPH03249946A (ja) * | 1990-02-28 | 1991-11-07 | Nard Inst Ltd | ラネーＮｉ系触媒の製法 |
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