CN1394839A - 从甘油化学合成乳特宁的方法 - Google Patents
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- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 229910052943 magnesium sulfate Inorganic materials 0.000 abstract description 2
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- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 abstract 1
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Abstract
一种合成乳特宁(3－羟基丙醛)的方法，包含使甘油在一硫酸盐触媒(例如硫酸钾或硫酸镁)存在下转化成丙烯醛和水，及使丙烯醛与水在一酸触媒存在下反应成乳特宁。
Description
技术领域
本发明是有关一种乳特宁的化学合成方法。
背景技术
Axelsson及其共事者报导了一广效抗微生物剂[Axelsson，L.，Chung，T.C.，Dobrogosz，W.J.，Lindgren，L.E.，″Discovery of anew antimicrobial substance produced by Lactobacillus reuteri，″FEMS microbiol.rev.，46，65，1987]，其是由乳酸菌Lactobacillasreuteri所产生，并命名为乳特宁(reuterin)。乳酸菌Lactobacillasreuteri生存于人类及动物的胃肠道，其在厌氧下代谢甘油可产生大量的乳特宁[Axelsson，L.，Chung，T.C.，Dobrogosz，W.J.，Lindgren，L.E.，″Production of a broad spectrum antimicrobial substanceby Lactobacillus reuteri，″Microb.ecol.，2，13l-136，1989；Talarico，T.L.，Dobrogosz，W.J.，″Production and isolation ofreuterin，a growth inhibitior produced by Lactobacillusreuteri，″Antimicrob.agents chemother.，32，1854-1858，1988]。乳特宁为3-羟基丙醛(3-hydroxypropinoaldehyde)，其为中性水可溶物质，能抑制细菌、酵母菌、霉茵及原虫。目前乳酸菌Lactobacillas reuteri及乳特宁仅应用于食品的保存及灭菌。
美国专利第5413960号揭示了L.reuteri在嫌氧状态下代谢甘油(下式I)可形成一低分子量，具有良好热稳定性的物质乳特宁(下式II)，乳特宁具有广效性(broad-spectrum antimicrobial effect)的抗菌作用。由于以L.reuteri代谢甘油产生乳特宁的产率及产量比较低，所需要的生产时间比较长，无法符合实际应用上的需求。
发明内容
为了克服上述的问题，本发明尝试以化学合成的方法来合成乳特宁，提供一种从甘油化学合成乳特宁(3-羟基丙醛)的方法，以提高乳特宁的产率及产量，符合实际应用上的需求。
本发明提供一种乳特宁的合成方法，包含下列步骤：a)使甘油在一硫酸盐触媒存在下转化成丙烯醛(下式III)和水；及b)使丙烯醛和水在一酸触媒存在下反应成乳特宁。
较佳的，本发明合成方法中的步骤a)包含使甘油蒸汽通过一固态硫酸盐触媒而生成含有丙烯醛及水蒸汽的气体混合物，及冷凝该气体混合物；及步骤b)包含将从步骤a)得到的冷凝液体导入一含有该酸触媒的水溶液中而于其中形成乳特宁。
较佳的，本发明的合成方法中的步骤b)形成乳特宁的反应是在50℃进行。
较佳的，本发明的合成方法进一步包含加热一液态甘油而产生该甘油蒸汽。
较佳的，本发明的合成方法进一步包含纯化步骤b)所得到的产物混合物而得到一实质上纯的乳特宁。更佳的，该纯化包含使用高效液态层析法(HPLC)。
较佳的，该硫酸盐触媒为硫酸镁或硫酸钾。
较佳的，该酸触媒为液态无机酸，例如0.6N硫酸水溶液。
依本发明方法所制备的纯化后的乳特宁的FT-IR、GC-MS及NMR分析的结果，与文献上所记载微生物合成乳特宁的各种图谱相符合，说明本发明可以得到相当纯的乳特宁，所以在实际应用中可以提高乳特宁的产率及产量。本发明方法亦可用于该环二聚体的制备。
附图说明
图1为一适用于本发明方法的实验室合成设备的示意图。
图2为依本发明方法所制备的纯化乳特宁的HPLC图谱。
图3为依本发明方法所制备的纯化乳特宁的GC-MS图谱。
图4为依本发明方法所制备的纯化乳特宁的13C-NMR图谱。图号说明10..高温炉 20..冷凝管 30..0.6N H2SO4溶液 40..水浴
具体实施方式较佳具体实施例的详细说明
本发明揭示了一从甘油化学合成乳特宁的方法，以下将由本发明的一较佳具体实施例来加以说明。如图1所示，首先在高温炉10中加热甘油(40mL)至340℃产生甘油蒸汽，让甘油蒸汽通过固体硫酸镁15(25g)，经催化后产生含丙烯醛的气体混合物，然后再将该气体混合物导入一冷凝管20而形成一液体，并滴入0.6N H2SO4溶液30(1000mL)中，在一温度维持在50℃的水浴40下反应3小时以进行乳特宁的合成。
以分析级的高效液相层析(high performance liquidchromatography，简称HPLC)来分析所获得的含乳特宁的产物混合物。HPLC光谱是被记录于一高效液相层析仪(HPLC TSP，P-100，RivieraBeach，FL33419，USA)，其中移动相溶液为acetonitrile与水(65∶35，V/V)的混合液，每升的混合液并加入027mL的浓硫酸使移动相溶液具有0.01N的硫酸浓度，取0.1mL的样品经0.25μm滤膜过滤后，将滤液注入一分析级离子交换管柱(长30cm，内径7.8mm，87H3，Transgenomic，Omaha，Nevada，USA)，以该移动相溶液0.7mL/min进行流洗(elution)。采用refractive index detector(RI2000-F，SFD，Torrance，California，USA)，检测溶离液(eluate)的吸收。结果显示在HPLC图谱中有2个波峰(peaks)：分别为乳特宁及未反应的甘油。计算得知甘油的转化率约为50％。发明人相信若能改善图1中的高温炉10的绝热系统、稳定温控效果，将能进一步提升甘油的转化率。
前述所获得的含乳特宁的产物混合物被进一步以制备级的HPLC管柱分离纯化。将10mL产物混合物注入一填充有100g Bio-Rad 50W-X8树脂的逆相色层层析管柱(长度30cm，内径3cm，粒径200μm-400μm)，其中移动相溶液为acetonitrile与水(60∶40，V/V)的混合液，每升的混合液并加入1.1g的trifluoroacetic acid进行流洗(elution)，并以收集器(SF-2100W，ADVANTEC，Dublin，California，USA)收集乳特宁产物。
以分析级的HPLC来分析所获得的纯化的含乳特宁。结果如图2所示，图谱中除了溶剂的波峰外，只有单一的乳特宁波峰，而不再有甘油的波峰。从图2可知经过分离纯化后，我们可以得到相当纯的乳特宁。
纯化后的乳特宁亦被进行FT-IR分析。结果显示，FT-IR图谱中有4个特征吸收峰，分别为：1050至1150cm-1(C-O group)；1720cm-1(C＝O group)；2880和1380cm-1(C-H group)；3450cm-1(O-H group)。
图3为纯化后的乳特宁进行GC-MS分析的结果。图3中，分子量57为丙酮溶剂的波峰，而分子量73与147分别为乳特宁单体(monomer)及其环二聚体(cyclic dimer)。图3结果显示，乳特宁在溶液中是与其环二聚体呈一平衡状态而同时存在，此与美国专利第5413960号的记载一致。易言之，本发明方法亦可用于该环二聚体的制备。
图4为纯化后的乳特宁的13C-NMR图谱，其中主要的化学位移(chemical shifts)在40、46、56、58、90和209ppm。其中209ppm是C＝O基团的特征值，而56、58、90是C-O基团的特征值，40、46则为C-C基团的特征值。
以上依本发明方法所制备的纯化后的乳特宁的FT-IR、GC-MS及NMR分析的结果，与文献上所记载微生物合成乳特宁的各种图谱相符合[T.L.Talarico，W.J.Dobrogosz，”Chemical Characterization ofAntimicrobial Substance Produced by Lactobacillus reuteri，”Antimicrobial Agents and Chemotherapy，vol.33，pp.674-679，1989]。
虽然本发明已参照较佳实施例披露于上，然而并非用于限定本发明。任何熟悉该领域者，在不脱离本发明的精神和范围内，可作出各种变更与润饰，因此本发明的保护范围以申请专利范围所界定的为准。
Claims (9)
1.一种合成乳特宁的方法，包含下列步骤：a)使甘油在一硫酸盐触媒存在下转化成丙烯醛和水；及b)使丙烯醛和水在一酸触媒存在下反应成乳特宁。
2.如权利要求1所述的方法，其中步骤a)包含使甘油蒸汽通过一固态硫酸盐触媒而生成含有丙烯醛及水蒸汽的气体混合物，及冷凝该气体混合物；及步骤b)包含将从步骤a)得到的冷凝液体导入一含有该酸触媒的水溶液中而于其中形成乳特宁。
3.如权利要求1或2所述的方法，其中该硫酸盐触媒为硫酸镁或硫酸钾。
4.如权利要求1、2或3所述的方法，其中该酸触媒为无机酸。
5.如权利要求4所述的方法，其中该无机酸为0.6N硫酸水溶液。
6.如权利要求1至5任一项所述的方法，其中步骤b)形成乳特宁的反应是在50℃进行。
7.如权利要求2至6任一项所述的方法，其进一步包含加热一液态甘油而产生该甘油蒸汽。
8.如权利要求1至7任一项所述的方法，其进一步包含纯化步骤b)所得到的产物混合物而得到一实质上纯的乳特宁。
9.如权利要求8所述的方法，其中该纯化包含使用高效液态层析法(HPLC)。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7396962B1 (en) | 2005-02-15 | 2008-07-08 | Arkema France | Process for dehydrating glycerol to acrolein |
| DE102008027350A1 (de) | 2008-06-07 | 2009-12-17 | Wolfgang Prof. Dr. Hölderich | Heterogenkatalysatoren für die Dehydratisierung von Glycerin |
| US7655818B2 (en) | 2005-02-15 | 2010-02-02 | Arkema France | Process for dehydrating glycerol to acrolein |
| FR3158110A1 (fr) | 2024-01-08 | 2025-07-11 | Arkema France | Procede de fabrication d’acroleine |
| FR3158111A1 (fr) | 2024-01-08 | 2025-07-11 | Arkema France | Procede de fabrication d’acroleine |
| FR3158112A1 (fr) | 2024-01-08 | 2025-07-11 | Arkema France | Procede de fabrication d’acroleine |
-
2001
- 2001-07-05 CN CN 01119982 patent/CN1394839A/zh active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7396962B1 (en) | 2005-02-15 | 2008-07-08 | Arkema France | Process for dehydrating glycerol to acrolein |
| US7655818B2 (en) | 2005-02-15 | 2010-02-02 | Arkema France | Process for dehydrating glycerol to acrolein |
| EP2377842A1 (en) | 2005-02-15 | 2011-10-19 | Arkema France | Process for dehydrating glycerol to acrolein |
| CN101119956B (zh) * | 2005-02-15 | 2012-02-15 | 阿肯马法国公司 | 使甘油脱水为丙烯醛的方法 |
| DE102008027350A1 (de) | 2008-06-07 | 2009-12-17 | Wolfgang Prof. Dr. Hölderich | Heterogenkatalysatoren für die Dehydratisierung von Glycerin |
| FR3158110A1 (fr) | 2024-01-08 | 2025-07-11 | Arkema France | Procede de fabrication d’acroleine |
| FR3158111A1 (fr) | 2024-01-08 | 2025-07-11 | Arkema France | Procede de fabrication d’acroleine |
| FR3158112A1 (fr) | 2024-01-08 | 2025-07-11 | Arkema France | Procede de fabrication d’acroleine |
| WO2025149416A1 (fr) | 2024-01-08 | 2025-07-17 | Arkema France | Procede de fabrication d'acroleine |
| WO2025149415A1 (fr) | 2024-01-08 | 2025-07-17 | Arkema France | Procede de fabrication d'acroleine |
| WO2025149414A1 (fr) | 2024-01-08 | 2025-07-17 | Arkema France | Procede de fabrication d'acroleine |
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