CN1299373A - 选择性氧化伯醇的方法 - Google Patents

选择性氧化伯醇的方法 Download PDF

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CN1299373A
CN1299373A CN99805863A CN99805863A CN1299373A CN 1299373 A CN1299373 A CN 1299373A CN 99805863 A CN99805863 A CN 99805863A CN 99805863 A CN99805863 A CN 99805863A CN 1299373 A CN1299373 A CN 1299373A
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扬·彼得·菠德卢格特
扬·马泰斯·耶滕
阿里·科内利斯·贝塞梅尔
亨德里克·阿伦德·范多伦
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Abstract

伯醇,特别是在碳水化合物中的伯醇可选择性地在低卤素方法中,通过使用过酸、在催化量的二叔烷基硝酰(TEMPO)和催化量的卤化物存在下被氧化成醛和羧酸。卤化物优选是溴化物且该方法可在接近中性或微碱性pH(5—11)下进行。所述过酸可通过过氧化氢或氧制备或再生。所述方法适合于制备糖醛酸或用于引入易于进行交联或衍生的醛基。

Description

选择性氧化伯醇的方法
本发明涉及在催化量的二-叔烷基硝酰化合物，特别是2,2,6,6-四甲基吡啶-1-酰(TEMPO)存在下使用氧化剂选择性氧化伯醇的方法。
这种方法可从Tetrahedron lett.34,1181-1184(1993)得知，该文献描述了单糖的氧化，其中非伯羟基被部分保护，在一两相溶剂体系(二氯甲烷和水)中使用次氯酸钠、溴化钾和2,2,6,6-四甲基吡啶-1-酰以制得对应的糖醛酸。WO95/07303介绍了一种在水性介质中以9-13的PH值、用次氯酸盐/2,2,6,6-四甲基吡啶-1-酰氧化碳水化合物的方法。在WO96/38484中介绍了用2,2,6,6-四甲基吡啶-1-酰氧化淀粉和纤维素及其它淀粉醚的羧甲基和羟乙基衍生物。
这些现有的氧化反应具有可选择性地进行的优点，其中伯醇的氧化大大好于仲醇。然而，这些公知的方法使用次氯酸盐作为实际的氧化剂且由此产生氯化物和一些氯化副产物：对于伯醇完全氧化成羧酸，使用两摩尔当量的次氯酸盐而得到两摩尔当量的氯化物。这是一个严重的缺陷，因此日益需要低氯或甚至是无氯的氧化方法。
现已发现，伯醇官能团的氧化可不使用等当量含氯化合物且可能使用过氧化氢作为最终的氧化剂。本发明的方法是由所附权利要求书的特征部分限定。
在下列说明中，为了简单的缘故，只使用TEMPO，但应理解的是，其它二叔烷基硝酰，例如4,4-二甲基噁唑烷-N-酰，2,2,5,5-四甲基吡啶-1-酰和4-羟基-TEMPO和其衍生物且在WO95/07303中介绍的那些物质可用于替代TEMPO。催化量的硝酰基于伯醇优选为0.1-2.5重量％，或相对于伯醇为0.1-2.5摩尔％。
在本发明中存在的卤化物用于再生TEMPO。所述卤化物可以是氯化物，但优选是溴化物。所述卤化物可这样地添加至反应混合物中，但也可以它的一种等同物或以一种分子卤素添加。通过过酸将卤化物离子氧化成分子卤素且该分子卤素使TEMPO再生。由此，TEMPO和卤化物两者仅需要以催化量存在。相对于伯醇，氯化物的催化量可以是0.1-40，优选为0.5-10摩尔％。
所述过酸可以是任一种过链烷酸例如过乙酸、过丙酸、过月桂酸等，一种取代的链烷酸例如过氧化三氟乙酸、一种选择性地取代的芳香过酸例如过苯甲酸或间-氯代过苯甲酸或一种无机过酸例如过硫酸或上述过酸的任一种盐，例如可以商品名Oxone市售购得的过氧化单硫酸钾。所述过酸可在氧化反应之前或在氧化反应过程中，在现场从一种前体例如对应的醛、(羧)酸、酸酐、酯或酰胺化物，例如四乙酰基-乙二胺，与一种合适的不含卤素的氧化剂，例如过氧化氢或氧反应形成。
本发明的方法使得伯醇首先氧化成对应的醛，且最终氧化成对应的羧酸。通常而言，所述第二氧化步骤，从醛至羧酸，比第一个步骤(即从醇氧化成醛)以更快的速率进行。在通常的实验条件下，含有的醛官能团的最大比率将在约10和15％之间(基于氧化反应可用的伯羟基的数目)。本方法特别适用于对醇中的伯羟基的选择性氧化，所述醇除了伯醇官能团之外，还有仲醇官能团，例如1,6-辛二醇、1,9-十八烷二醇、糖醇、苷、且特别是具有伯醇官能团的碳水化合物例如葡聚糖(淀粉，纤维素)，呋喃果聚糖，半乳聚糖，(半乳)甘露聚糖等。适合用于本方法的氧化反应的特定化合物是羟烷基化的，特别是羟烷基化的碳水化合物例如羟乙基淀粉或羟乙基菊粉。这些衍生物导致制备甲酰甲基和羧甲基碳水化合物的一种替代物。
含伯羟基的碳水化合物的氧化得到含带有完整环状系统的醛和/或羧酸的对应碳水化合物。例子包括α-1,4-葡聚糖-6-醛，β-2,1-果聚糖-6-醛和β-2,1-果聚糖-1-醛，以及对应的羧酸。其中这些产物仍然包括醛，它们可用于官能化碳水化合物的中间体，其中醛基团进一步与例如胺类化合物等反应。它们也可用作交联碳水化合物的中间体，其中醛基进一步与二胺类试剂反应。
实施例1：甲基α-D-吡喃葡糖苷的氧化
将1克甲基α-D-吡喃葡糖苷(5.15mmol)于室温下溶解在60毫升水中。将200毫克NaBr(1.94mmol)，20毫克TEMPO(0.13mmol)，10毫克EDTA(用作稳定和氧化剂)和2.5克NaHCO3添加至该溶液中。过乙酸(1.32mmol/ml)以每10分钟200μl的量加入直至根据100％氧化成6-羧酸(14.6mmol)的理论计算的剩余量得以加完。通过使用PH-stat添加1M NaOH将PH值保持在7。反应时间是8小时。使用Blumenkrantz方法用半乳糖醛酸作为参比测得的氧化度为95％。高效阴离子交换色谱(HPAEC)显示，氧化度大于95％。没有检测到比糖醛酸还高的峰值以及痕量的原材料。实施例2：α-D-吡喃葡糖苷磷酸盐的氧化
将1.97克α-D-吡喃葡糖苷磷酸盐(2K+.C6H11O9P2-.2H2O,5.5mmol)于室温下溶解在60毫升水中。将210毫克KBr(1.76mmol),20毫克TEMPO(0.13mmol),10毫克EDTA和2.5克NaHCO3添加至该溶液中。过乙酸(10ml,1.69mmol/ml)以每10分钟200μl的量加入。通过使用一个PH-stat添加2MNaOH将PH值保持在8。16小时后完成反应。在添加甲醇后，产物从混合物中结晶而得到α-D-吡喃葡糖苷酸1-磷酸盐(3K+.C6H8O10P2-.5H2O,1.90g,4.0mmol,73％)。NMR(500 Mhz,D2O,in ppm):1Hδ3.32(dd,H-4,J3,4=9.5Hz,J4,5=9.9Hz),3.35(m,H-2,Jp,H2=1.8Hz,J1,2=3.4Hz,J2,3=9.5Hz),3.62(dd,H-3,J2,3=9.5Hz,J3,4=9.5Hz),3.99(d,H-1,J4,5=9.9Hz),5.30(dd,H-1,JP,H1=9.5Hz,J1,2=9.9Hz),13Cδ71.4(C-2),71.5(C-3,C-4),72.4(C-5),93.0(C-1),176.6(C-6)。实施例3：D-葡糖苷酸的氧化
将1.94克D-葡糖苷酸(10mmol)于室温下溶解在50毫升水中。将196毫克KBr(1.65mmol),30毫克TEMPO(0.20mmol),10毫克EDTA和1.0克NaHCO3添加至该溶液中。过乙酸(8ml,1.69mmol/ml)以每10分钟200μl的量加入。通过使用PH-stat添加2M NaOH将PH值保持在8。16小时后完成反应。将反应混合物用浓盐酸酸化至PH3.4且将产物结晶以得到D-葡糖二酸，单钾盐(K+.C6H9O8P2-.H2O,1.55g,0.62mmol,62％)。FT-IR(in cm-1):3379(s),3261(s),2940(m),1738(s),1453(m),1407(m),1385(m),1342(m),1267(m(,1215(m),1108(s),1050(m),862(m),657(m)。实施例4：淀粉在PH5下的氧化
将1克土豆淀粉(6.17mmol)于100℃下在60毫升水中胶凝化。将200毫克NaBr(1.94mmol),20毫克TEMPO(0.13mmol),10毫克EDTA和2.5克乙酸钠添加至该溶液中。过乙酸(1.51mmol/ml)以每10分钟200μl的量加入直至根据100％氧化成6-羧酸(13.6mmol)的理论计算的剩余量得以加完。通过使用PH-stat添加1.0M NaOH将PH值保持在5。反应时间是8小时。氧化度(Blumenkrantz-半乳糖醛酸)26％6-羧基淀粉。实施例5：淀粉在PH6下的氧化
将1克土豆淀粉(6.17mmol)于100℃下在60毫升水中胶凝化。在室温下将200毫克NaBr(1.94mmol),20毫克TEMPO(0.13mmol),10毫克EDTA和1.25克NaH2PO4和1.25克Na2HPO4添加至该溶液中。过乙酸(1.51mmol/ml)以每10分钟200μl的量加入直至根据100％氧化成6-羧酸(13.8mmol)的理论计算的剩余量得以加完。通过使用PH-stat添加1.0 M NaOH将PH值保持在6。反应时间是8小时。氧化度(Blumenkrantz-半乳糖醛酸)40％6-羧基淀粉。实施例6：淀粉在PH7下的氧化
将1克土豆淀粉(6.17mmol)于100℃下在60毫升水中胶凝化。在室温下将200毫克NaBr(1.94mmol),20毫克TEMPO(0.13mmol),10毫克EDTA和2.5克NaCO3添加至该溶液中。过乙酸(1.35mmol/ml)以每10分钟200μl的量加入直至根据100％氧化成6-羧酸(18.4mmol)的理论计算的剩余量得以加完。通过使用PH-stat添加1.0 M NaOH将PH值保持在7。反应时间是11.5小时。使用Blumenkrantz方法用半乳糖醛酸作为参照而测得的氧化度为95％6-羧基淀粉。用高效阴离子交换色谱测得的氧化度86％6-羧基淀粉。实施例7：淀粉在PH8下的氧化
重复实施例6，然而将PH值保持在8。消耗的过乙酸是13.9mmol。氧化度(Blumenkrantz-聚半乳糖醛酸)是91％6-羧基淀粉。实施例8：淀粉在PH9下的氧化
重复实施例6，然而将PH值保持在9。消耗的过乙酸是11.9mmol。氧化度(Blumenkrantz-聚半乳糖醛酸)是90％6-羧基淀粉。实施例9：淀粉在PH10下的氧化
重复实施例6(使用2.5克Na2HPO4代替NaHCO3)。消耗的过乙酸是(1.35mmol/ml)是14.3mmol。氧化度是37％6-羧基淀粉。

Claims (8)

1、一种在催化量的二叔烷基硝酰存在下使用氧化剂氧化一种伯醇的方法，其特征在于，将所述醇在催化量的卤化物存在下使用一种过酸或其盐或前体进行氧化。
2、根据权利要求1所述的方法，其中卤化物是溴化物。
3、根据权利要求1或2所述的方法，其中所述二叔烷基硝酰是2,2,6,6-四甲基吡啶-1-酰。
4、根据权利要求1-3任一所述的方法，其中使用PH5-11，特别是PH7-10。
5、根据权利要求1-4任一所述的方法，其中所述过酸是一种过链烷酸，特别是过乙酸。
6、根据权利要求1-5任一所述的方法，其中所述过酸是由过氧化氢在现场制得。
7、根据权利要求1-6任一所述的方法，其中所述伯醇是一种碳水化合物。
8、根据权利要求1-6任一所述的方法，其中所述伯醇是一种羟烷基化碳水化合物。
CNB998058637A 1998-05-07 1999-05-04 选择性氧化伯醇的方法 Expired - Fee Related CN1141322C (zh)

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