CN100341884C - 用于制备烷基苷类的方法 - Google Patents
用于制备烷基苷类的方法 Download PDFInfo
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- CN100341884C CN100341884C CNB2005100728363A CN200510072836A CN100341884C CN 100341884 C CN100341884 C CN 100341884C CN B2005100728363 A CNB2005100728363 A CN B2005100728363A CN 200510072836 A CN200510072836 A CN 200510072836A CN 100341884 C CN100341884 C CN 100341884C
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- Prior art keywords
- alcohol
- glyc
- acid
- glycosides
- reactor
- Prior art date
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- 229930182470 glycoside Natural products 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims description 36
- -1 alkyl glycosides Chemical class 0.000 title claims description 7
- 150000002338 glycosides Chemical class 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000376 reactant Substances 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229920002472 Starch Polymers 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 5
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 5
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
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- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
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- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-PQMKYFCFSA-N alpha-D-mannose Chemical compound OC[C@H]1O[C@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-PQMKYFCFSA-N 0.000 claims description 3
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 claims description 3
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 3
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- 239000001814 pectin Substances 0.000 claims description 3
- 235000010987 pectin Nutrition 0.000 claims description 3
- 150000002972 pentoses Chemical class 0.000 claims description 3
- 229960003487 xylose Drugs 0.000 claims description 3
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 claims description 2
- PVXPPJIGRGXGCY-DJHAAKORSA-N 6-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@](O)(CO)O1 PVXPPJIGRGXGCY-DJHAAKORSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- 229920000945 Amylopectin Polymers 0.000 claims description 2
- 229920000856 Amylose Polymers 0.000 claims description 2
- 229920002101 Chitin Polymers 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims description 2
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-CBPJZXOFSA-N D-Gulose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-CBPJZXOFSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-IVMDWMLBSA-N D-allopyranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-IVMDWMLBSA-N 0.000 claims description 2
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- ZGVNGXVNRCEBDS-UHFFFAOYSA-N D-hamamelose Natural products OCC(O)C(O)C(O)(CO)C=O ZGVNGXVNRCEBDS-UHFFFAOYSA-N 0.000 claims description 2
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 claims description 2
- YTBSYETUWUMLBZ-QWWZWVQMSA-N D-threose Chemical compound OC[C@@H](O)[C@H](O)C=O YTBSYETUWUMLBZ-QWWZWVQMSA-N 0.000 claims description 2
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- 206010056474 Erythrosis Diseases 0.000 claims description 2
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- 229920001202 Inulin Polymers 0.000 claims description 2
- WQZGKKKJIJFFOK-VSOAQEOCSA-N L-altropyranose Chemical compound OC[C@@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-VSOAQEOCSA-N 0.000 claims description 2
- SHZGCJCMOBCMKK-DHVFOXMCSA-N L-fucopyranose Chemical compound C[C@@H]1OC(O)[C@@H](O)[C@H](O)[C@@H]1O SHZGCJCMOBCMKK-DHVFOXMCSA-N 0.000 claims description 2
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- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 claims description 2
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 claims description 2
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- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-N 0.000 claims description 2
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
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- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
- C07H15/06—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical being a hydroxyalkyl group esterified by a fatty acid
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- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
- C07H15/10—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical containing unsaturated carbon-to-carbon bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
本发明涉及按照以下通用路线由单苷类、寡苷类或多苷类和醇制备烷基多苷类的方法：(Glyc-O)zH+R1-OH→(Glyc-O)z’R1其中z≥1，z’≤z，优选1-10，(Glyc-O)-是苷基，R1是任选含有重键和/或杂原子的烃基，该方法包括在该醇的超临界条件下进行反应，优选在高于临界参数至少5%的压力和温度下进行反应，该醇既作为溶剂又作为反应物。
Description
技术领域
本发明涉及由单苷类、寡苷类或多苷类和醇制备烷基多苷类的方法。
背景技术
苷是一大类植物性物质和合成化合物，它们通过与水或稀酸一起煮沸，或者在糖苷酶的作用下，裂解成一个或多个糖(单糖或寡糖)和其它化合物。糖类通过糖苷键(通常为醚键)内的氧原子和半缩醛碳原子连接，成为完整缩醛。(Rmpp Lexikon Chemie-Version 2.0，Stuttgart/New York：Georg Thieme Verlag 1999)。
苷的单体通常是单糖，例如葡萄糖(最常见)或半乳糖、甘露糖、果糖，尤其是己糖或戊糖阿拉伯糖、木糖、核糖：另外，还存在只见于苷中的糖，例如毛地黄糖、磁麻糖等。当苷的糖基是葡萄糖时，该衍生物称为葡糖苷；类似地，果糖苷是以果糖为糖成分的苷，半乳糖苷是以半乳糖为糖成分的苷。(Rmpp Lexikon Chemie-Version 2.0，Stuttgart/New York：Georg Thieme Verlag 1999)。
甲基苷类是合成烷基苷类的原料。它们是由糖半缩醛制备的完整缩醛。类似地，相应的缩酮由非还原性糖形成(lit.：A.T.J.W.deGoede，F.Van Rantwijk，H.Van Bekkum，Starch/Strke 47(1995)233-237)。缩酮对于化妆品工业而言是一类极其重要的物质。到目前为止，最重要的化合物(可能在进一步修饰后)尤其是用作具有良好泡沫性质的非离子表面活性剂，用作乳化剂或者用作增稠剂。这些化合物的优点在于它们的低粘膜刺激可能和它们的生物可降解性。
烷基葡糖苷类的经典合成通过在酸性催化剂的存在下糖类和醇类反应而实现(Fischer glycosidation；lit.：A.F.Bochkov，G.E.Zaikov：The Chemistry of the O-Glycosidic Bond，Pergamon Press，Oxford 1979，210pp)。为了使互不混溶的反应物能发生反应，将混合物长时间保持在高温下，并将所形成的水除去。即使是简单的糖水解都需要使用1M硫酸和100℃下数小时的相对激烈的条件(这是含己糖的多糖的情况；lit.：Frieder W.Lichtenthaler，in Ullmann’s Encyclopedia of IndustrialChemistry，“Carbohydrates”)。但是，在此过程中不能避免糖的部分分解。一般而言，产物成分在很大程度上取决于所选择的催化剂。在两阶段合成中，可以首先制备具有短烷基链的苷，随后通过在酸的存在下进行缩醛转移(transacetalization)而将所述短烷基链交换为另一烷基。
用于苷类烷基化的典型催化剂是硫酸和对甲苯磺酸，如US3772269和US 3375243所述。这类强酸引起产物强烈着色，这使得产物的处理(workup)成为必需。另外，强有机酸和弱有机碱的混合盐的使用是公知的(US 5432269)，但是以此方式制备的产物也强烈着色而且可能含有游离有机碱。多元羧酸盐(US 4898934)和羟基羧酸盐(US 4465828)也被作为催化剂使用。然而，当对该反应混合物进行浓缩时，由于热应力，在浓酸的存在下不可避免地获得着色产物。因此，在所有的情况下，接下来都必需进行产物脱色步骤(例如用H2O2)。
最简单和最廉价的苷是甲基葡糖苷(见路线1中的式II)，它的制备已经公知一段时间：参见Rmpp Chemie Lexikon，标题：α-methylglucoside：Preparation by the action of methanol on glucose inthe presence of HCl ora cation exchanger.另外还形成β-甲基葡糖苷。
路线1：
这种合成还在许多专利中得到描述，例如US 2276621(公开日：1942年3月17日)。该反应在糖，例如淀粉的存在下，在作为醇成分同时又作为溶剂的甲醇中进行。所使用的催化剂是无机酸，例如硫酸。糖水解产生葡萄糖，并在催化剂的存在下获得甲基葡糖苷。
JP-A-06-092984描述了基于阳离子交换树脂的固定催化剂系统用于制备甲基葡糖苷的用途，据说其能够制备仅轻微着色的产物。与之类似，Amberlyst 15的使用在DE-A-3611035中得到描述。
FR-1114382描述了在盐酸的存在下马铃薯淀粉和甲醇的反应。进一步的反应需要加入稀硫酸并随后脱色。
根据现有技术，直接从寡苷类或多苷类制备烷基苷类的一种方法只有在通过在醇中在催化剂的存在下的水解裂解(酶促水解裂解，例如用糖苷酶，或者酸催化的化学水解裂解)而进行的费力的方法中才是可能的。当使用上述常规方法时，得到多种副产物，以及其中一些是严重着色的产物(主要是未反应的糖类)，其结果是需要对产物作进一步的处理。
烷基多苷类的制备也已得到描述，例如在EP-B-0970097。为了形成完整缩醛，在作为催化剂的硫酸和氢氧化钠或碳酸钠的混合物的存在下，使单糖和过量的醇在高温和标准压力下反应。尽管通过选择催化剂混合物使得反应混合物的中和一般是不需要的，但在这种情况下可能还是必须加入碱。所使用的醇类可以是任何的一羟基或多羟基的伯醇或仲醇。酶的苷化也是公知的(JP-A-9087294、EP-A-725144、JP-A-8067690、JP-A-7087992)。
极为不同的糖类，例如麦芽糖，甚至是聚合性质的糖类的反应也是公知的。在US-A-2002/099185中描述了麦芽寡糖类与醇或硫醇的酸催化反应。
然而，所有这些制备方法都是相应的烷基苷类的耗时的分批合成，其中由于反应物质长时间暴露于苛刻的条件下，因此可能得到大量导致产物严重着色的副产物。
所以，仍需要简单和廉价的烷基苷类合成方法，其中可以通过糖类、寡苷类或多苷类的直接反应，连续或者分批地以高时空收率制备这些产物，尽可能地不添加催化剂或活化剂，这样就不需要进一步处理，例如漂白。
发明内容
本发明的目的是提供这样的方法。
已令人惊奇地发现，天然和非天然的苷类，以及寡苷类和多苷类在高温和高压下(这两个参数都至少必须达到该醇的临界值)通过羰基与醇反应，这最终相当于简单的半缩醛反应生成完整缩醛。还已发现，多苷类在这些条件下可以裂解成它们的单体，苷类，以形成完全缩醛化的单体(参见路线1)。含酸性基团的苷类，例如果胶，在所选择的条件下还被酯化。
本发明提供根据以下通用路线由单苷类、寡苷类或多苷类和醇制备烷基多苷类的方法：
(Glyc-O)zH+R1-OH→(Glyc-O)z’R1
其中
z≥1，
z’≤z，优选1-10，
(Glyc-O)-是苷基，
R1是任选含有重键和/或杂原子的烃基，该方法包括在该醇的超临界条件下进行反应，优选该超临界压力和超临界温度的参数比该醇的临界参数至少高5％。
本发明进一步提供权利要求的主题。
在本发明的单苷类、寡苷类和多苷类的反应中，通过按照通用路线2在超临界的醇中反应而获得完整缩醛：
路线2：
多苷和醇的反应
(Glyc-O)zH+R1-OH→(Glyc-O)z’R1
其中
z≥1，
z’≤z，优选1-10，
当z＝1时，(Glyc-O)zH是醛糖，例如丙糖、四糖、戊糖、己糖，尤其是赤藓糖、苏糖、核糖、阿拉伯糖、木糖、来苏糖、阿洛糖、阿卓糖、葡萄糖、甘露糖、古洛糖、艾杜糖、半乳糖、果糖和苷类衍生物，尤其是葡糖胺、N-乙酰葡糖胺、鼠李糖、岩藻糖、2-脱氧-D-赤式戊糖、葡糖醛酸、半乳糖醛酸、脂肪(adipose)、金缕梅糖和四酰基葡萄糖，
当z＞1时，(Glyc-O)zH是上述单体的低聚体或多聚体，它们相同或不同，即寡苷或多苷，尤其是蔗糖、海藻糖、棉子糖、乳糖、纤维二糖、麦芽糖、异麦芽酮糖(isomaltulose)、乳果糖、环糊精、直链淀粉、纤维素、壳多糖、淀粉、菊粉、支链淀粉、果胶、葡聚糖。
尤其优选的式(Glyc-O)zH起始化合物是葡萄糖及其化合物。
原则上所有的醇都是合适的反应物同时又是溶剂。在可根据本发明使用的通式R1-OH的伯醇或仲醇中
R1是任选分支的任选含有双键的烃基，或者是具有1-30个碳原子，尤其是1-18个碳原子，优选1-4个碳原子的羟烷基、烷氧基，并且该基团还可以含有脂环或杂环成分，所述环是饱和、不饱和或芳香性的，具有3-10个原子，优选4-6个原子的环大小，其可以进一步带有1-30个碳原子，优选1-18个碳原子，尤其是＜C10，更优选＜C5，的饱和或不饱和烃取代基，如甲醇、乙醇、丙醇。
表1以举例方式列举了一些化合物。
适于本发明的方法的通式R1-OH的化合物尤其是烷醇，优选甲醇、乙醇、丙醇、异丙醇、辛醇、十二烷醇、十六烷醇、十八烷醇和2-乙基己醇，还有多元醇，尤其是乙二醇、二乙二醇、聚醚、丙三醇和三羟甲基丙烷。也可以使用氨基醇，如乙醇胺、二乙醇胺和三乙醇胺，以及芳香醇，尤其是苯酚、苯甲醇和邻苯二酚，以及脂环醇，尤其是环戊醇和环己醇，还有不饱和醇，如己烯醇、十六碳烯醇和十八碳烯醇。在本发明的上下文中也可以使用合适的相互混合的醇，在这种情况下当一种醇成分达到超临界状态时在某种程度上已足够。
任选地该反应可以在合适的均相和非均相催化剂的存在下进行，所述催化剂选自质子酸，尤其是盐酸、硫酸、磷酸、醋酸、柠檬酸，或者选自盐类，尤其是AlCl3、LiClO4、LiCl、ZnCl2、BiCl3、Ti(OiPr)4(OiPr＝异丙醇盐)、稀土元素七氟二甲基辛二酸盐(＝fod)和三氟甲磺酸盐(＝OTf)，尤其是Yb(fod)3、Eu(fod)3、Sc(OTF)3、Yb(OTF)3，或者选自离子交换剂，尤其是Amberlyst-15，或者选自缓冲剂，尤其是Na3PO4/H3PO4。优选地，使用单苷类、寡苷类或多苷类在醇中的高浓度悬浮液实现直接反应，优选不添加活化剂或均相催化剂。
根据本发明使用的装置为具有搅拌器和泵的合适的反应器，所述搅拌器用于反应组分的最初的加料，所述泵用于将醇压缩至临界压力或临界压力以上。例如，带有悬浮球阀的合适的泵由LEWA供应。为了确保反应，醇的临界温度和临界压力两个值都必须达到，并且优选超过两个临界值。为了获得足够的反应速率，临界参数优选超过5-15％。表1列举了醇的临界参数的一些实例。反应在可加热的可连续或分批操作的反应器中进行。
表1
所选择的反应醇的临界数据：
| 醇 | Tc/K | Pc/巴 |
| 甲醇 | 512.6 | 80.9 |
| 乙醇 | 513.9 | 61.4 |
| 正丙醇 | 536.8 | 51.7 |
| 2-丙醇 | 508.4 | 47.6 |
| 丁醇 | 563.0 | 44.2 |
| 辛醇 | 625.5 | 28.6 |
| 十六醇 | 770.0 | 16.1 |
| 十八醇 | 790.0 | 12.8 |
| 丙三醇 | 726.05 | 66.9 |
Tc＝临界温度
Pc＝临界压力
根据本发明所使用的装置在附图1中示意性地显示。首先将反应物装于合适的搅拌容器(A)中。由合适的泵(B)将混合物从该容器传送至反应器(C)中。该泵能够使该混合物在A中达到式II的醇的临界压力或临界压力以上。加热器(D)用于将反应器(C)加热至高于或等于该醇的临界温度。在反应器(C)的出口，阀(E)可以用于调节反应装置中的压力。另外，这样可以个别地调节特定苷或苷/多苷/寡苷混合物的停留时间，因此可以将降解减之最小。为了将副产物减至最少，可以将来自贮存器(F)的包含纯醇的载体流通过泵B1使用预热器(G)加热至100℃-800℃的温度，优选至少达到临界温度。在混合点(H)，载体流(CS)和反应物流(RS)混合并供应给反应器。CS/RS的比值在0/100至99/1的宽范围内，优选20/80至80/20。当所选择的预热温度足够高，使得混合点已经达到反应温度时，就必须将反应器中的温度梯度调节至足够低的水平以防止碳化。
对反应产物的鉴定，尤其已发现GC、GC-MS、HPLC和MALDI是合适的分析方法。
附图说明
图1是用于制备烷基苷类的方法的示意流程图，其中各符号具有如下含义：A-容器，B、B1-泵，C-反应器，D-加热器，E-阀，F-载体流贮存器，G-载体流预热器，H-混合点。
具体实施方式
在所有的实施例中，试验后立即通过NMR和GC/MS进行分析。所有的实施例均在如附图1所示的装置中进行。为了传送反应混合物，使用带有HK 8mm泵头的LEWA EK08泵。
应用实施例1：
甲基葡糖苷的制备：
首先将甲醇和葡萄糖的混合物加料于搅拌容器A中。葡萄糖部分为甲醇部分的30％。将混合物在120巴的压力下通过合适的泵B连续传送至反应器C。通过加热器D将管状反应器C加热至160℃的温度。使用预热器G将来自贮存器F的包含纯甲醇的载体流加热至约300℃。在混合点H，使载体流和反应物流混合并供应给反应器。预热温度足够高，使得混合点已经达到反应温度，所以使反应器中的温度梯度足够低以防止在壁上碳化。在该管状反应器内的停留时间为约2分钟。在控制阀E的帮助下，将压力保持在上述的目标值。在系统的出口收集反应产物混合物。根据HPLC，产物混合物含有3％的产物。
应用实施例2：
甲基果糖苷的制备
首先将甲醇和果糖的混合物加料于搅拌容器A中。果糖部分为甲醇部分的30％。将混合物在120巴的压力下通过合适的泵B连续传送至反应器C。通过加热器D将管状反应器C加热至160℃的温度。使用预热器G将来自贮存器F的包含纯甲醇的载体流加热至约300℃。在混合点H，使载体流和反应物流混合并供应给反应器。预热温度足够高，使得混合点已经达到反应温度，所以使反应器中的温度梯度足够低以防止在壁上碳化。在该管状反应器内的停留时间为约2分钟。在控制阀E的帮助下，将压力保持在上述的目标值。在系统的出口收集反应产物混合物。根据HPLC，产物混合物含有4％的产物。
应用实施例3：
乙基葡糖苷的制备：
首先将乙醇和葡萄糖的混合物加料于搅拌容器A中。葡萄糖部分为乙醇部分的30％。将混合物在120巴的压力下通过合适的泵B连续传送至反应器C。通过加热器D将管状反应器C加热至150℃的温度。使用预热器G将来自贮存器F的包含纯乙醇的载体流加热至约280℃。在混合点H，使载体流和反应物流混合并供应给反应器。预热温度足够高，使得混合点已经达到反应温度，所以使反应器中的温度梯度足够低以防止在壁上碳化。在该管状反应器内的停留时间为约2分钟。在控制阀E的帮助下，将压力保持在上述的目标值。在系统的出口收集反应产物混合物。根据HPLC，产物混合物含有10％的产物。
Claims (23)
1、用于按照以下通用路线由单苷类、寡苷类或多苷类和醇制备烷基多苷类的方法：
(Glyc-O)zH+R1-OH→(Glyc-O)z’R1
其中
z≥1，
z’≤z，
(Glyc-O)-是苷基，
R1是任选含有重键和/或杂原子的烃基，该方法包括在该醇的超临界条件下进行反应。
2、如权利要求1所述的方法，其中z’为1-10。
3、如权利要求1所述的方法，其中该反应在超临界压力和超临界温度下进行。
4、如权利要求3所述的方法，其中该超临界压力和超临界温度的参数比该醇的临界参数至少高5％。
5、如权利要求1-4之任一项所述的方法，其中该反应连续进行或分批进行，并且反应混合物在反应器中的停留时间为1秒至24小时。
6、如权利要求5所述的方法，其中反应混合物在反应器中的停留时间为1秒至1小时。
7、如权利要求6所述的方法，其中反应混合物在反应器中的停留时间为1秒至5分钟。
8、如权利要求1-4之任一项所述的连续方法，其中将预热至100℃至800℃的温度的醇的载体流在反应器进口上游与反应物流混合。
9、如权利要求8所述的方法，其中将预热至至少达到该醇的临界温度的醇的载体流在反应器进口上游与反应物流混合。
10、如权利要求1-4之任一项所述的方法，其中
当z＝1时，(Glyc-O)zH是醛糖，并且
当z＞1时，(Glyc-O)zH相同或不同，且为寡苷或多苷。
11、如权利要求10所述的方法，其中所述醛糖是丙糖、四糖、戊糖、己糖，且所述寡苷或多苷为蔗糖、海藻糖、棉子糖、乳糖、纤维二糖、麦芽糖、异麦芽酮糖、乳果糖、环糊精、纤维素、壳多糖、淀粉、菊粉、果胶、葡聚糖。
12、如权利要求11所述的方法，其中所述淀粉为直链淀粉或支链淀粉。
13、如权利要求11所述的方法，其中所述醛糖是赤藓糖、苏糖、核糖、阿拉伯糖、木糖、来苏糖、阿洛糖、阿卓糖、葡萄糖、甘露糖、古洛糖、艾杜糖、半乳糖、果糖和苷衍生物。
14、如权利要求13所述的方法，其中所述醛糖是葡糖胺、N-乙酰葡糖胺、鼠李糖、岩藻糖、2-脱氧-D-赤式戊糖、葡糖醛酸、半乳糖醛酸、脂肪、金缕梅糖和酰基葡萄糖。
15、如权利要求1-4之任一项所述的方法，其中所使用的醇是至少一种通式R1-OH的化合物，其中R1是任选分支的任选含有双键和/或杂原子的烃基，或者是具有1-30个碳原子的羟烷基、烷氧基。
16、如权利要求15所述的方法，其中R1是具有1-18个碳原子的羟烷基、烷氧基。
17、如权利要求16所述的方法，其中R1是具有1-4个碳原子的羟烷基、烷氧基。
18、如权利要求1-4之任一项所述的方法，其中所使用的醇为选自下组中的至少一种化合物：甲醇、乙醇、丙醇、异丙醇、丁醇、己醇、辛醇、癸醇、十二醇、十六醇、十八醇、乙二醇、丙三醇、丙二醇。
19、如权利要求18所述的方法，其中至少一种醇成分达到或者超过超临界条件。
20、如权利要求1-4之任一项所述的方法，其中该反应在合适的均相和非均相催化剂的存在下进行，所述催化剂选自质子酸；或者选自盐类；或者选自离子交换剂；或者选自缓冲剂。
21、如权利要求20所述的方法，其中所述质子酸是盐酸、硫酸、磷酸、醋酸、柠檬酸；所述盐类是AlCl3、LiClO4、LiCl、ZnCl2、BiCl3、Ti(OiPr)4、稀土元素七氟二甲基辛二酸盐和三氟甲磺酸盐，其中OiPr代表异丙醇盐；所述离子交换剂是Amberlyst-15；且所述缓冲剂是Na3PO4/H3PO4。
22、如权利要求21所述的方法，其中所述盐类是Yb(fod)3、Eu(fod)3、Sc(OTf)3或Yb(OTf)3，其中fod代表七氟二甲基辛二酸盐，且OTf代表三氟甲磺酸盐。
23、权利要求1-4之任一项所述的方法，其中(Glyc-O)zH是葡萄糖，而R1-OH是甲醇。
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| CN106518935B (zh) * | 2016-10-26 | 2019-05-21 | 陕西国防工业职业技术学院 | 一种3,6-二去氧-3-氨基-l-艾杜糖及其衍生物的合成方法 |
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| EP3897143A1 (en) * | 2019-01-29 | 2021-10-27 | Ecolab USA Inc. | Use of cationic sugar-based compounds for microbial fouling control in a water system |
| CA3128188C (en) * | 2019-01-29 | 2023-10-17 | Ecolab Usa Inc. | Use of cationic sugar-based compounds as corrosion inhibitors in a water system |
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- 2005-04-25 US US11/113,750 patent/US7626006B2/en not_active Expired - Fee Related
- 2005-05-07 AT AT05009987T patent/ATE346077T1/de not_active IP Right Cessation
- 2005-05-07 ES ES05009987T patent/ES2275250T3/es active Active
- 2005-05-07 EP EP05009987A patent/EP1627882B1/de not_active Not-in-force
- 2005-05-07 DE DE502005000198T patent/DE502005000198D1/de active Active
- 2005-05-23 CN CNB2005100728363A patent/CN100341884C/zh not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| ATE346077T1 (de) | 2006-12-15 |
| DE102004025195A1 (de) | 2005-12-08 |
| CN1699387A (zh) | 2005-11-23 |
| DE502005000198D1 (de) | 2007-01-04 |
| US20050261484A1 (en) | 2005-11-24 |
| EP1627882A1 (de) | 2006-02-22 |
| JP2005336163A (ja) | 2005-12-08 |
| US7626006B2 (en) | 2009-12-01 |
| EP1627882B1 (de) | 2006-11-22 |
| ES2275250T3 (es) | 2007-06-01 |
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