CN1104414C - 生产鸢尾酮的方法 - Google Patents
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- C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
- C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
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Abstract
本发明描述了一种通过鸢尾酮前体的化学氧化制备鸢尾酮的方法,包括处理从下列组中选出的鸢尾根状茎底物:鸢尾根状茎、这种根状茎的部分、鸢尾提取物、鸢尾提取物废物、任何含有鸢尾酮前体或其混合物的植物组织。
Description
目前,可通过溶剂提取或蒸汽蒸馏的方法从鸢尾的任何种优选IrisPallida或德国鸢尾(Iris germanica)的根状茎中提取鸢尾酮。在培育2-3年后,收获根状茎并在室温下保存3-5年。在这段成熟期,鸢尾酮从其前体中释放出来(W.Krick,F.-J.Marner及L.Jaenicke,N.Naturforch.1983,38c 179-184)。通过根状茎粉的蒸汽蒸馏物(以鸢尾脂的形式)或溶剂提取物(形成类树脂)中回收鸢尾酮,得到调味剂和香料工业中很有价值的鸢尾物质。
长期保存既繁重、昂贵、需要大量存储空间又导致在不可控的降解反应中失去部分的异构体。对这种没有效率且耗时的成熟期,人们已提出多种解决方法。Buono等人的第一个提议(FR-2620702,24/3/89),将含鸢尾酮前体的鸢尾根状茎的亲脂提取物在有机溶剂中用KMnO4氧化。在此方法中,前体提取工作很繁重,而且由于其异常的下游加工(综合加工),即在氧化之前提取前体,所以所得产物的质量与常规优选的鸢尾脂或纯净物(Absolute)有很大的差异。在FR-2653637,3/5/91中Baccou等公开了一种把成熟期降低至两个月的方法,其中对幼嫩即未成熟的鸢尾根状茎以离子辐射进行预处理;但其产率很难达到由2-3年储存期成熟所得的鸢尾酮含量(<400毫克/千克干根茎)。Gil等公开了以Botryonia属的真菌(EP 0443925;23/8/91)或以过氧化物酶类(EP 0443 926;28/8/91)进行根状茎的亲脂提取物的生物转化,这些方法能得到前体的很好的生物转化;但其具有预溶剂提取的缺点因此产物质量与优选的鸢尾脂有差异。Belcour等利用在有植物细胞培养基(EP 0353 683,US4,963,480)存在的情况下,以肠杆菌科的细菌进行鸢尾根状茎粉的生物转化,从其前体中释放出鸢尾酮,而且经蒸汽蒸馏之后产生了高含量鸢尾酮的优异鸢尾脂。其缺点是用相当昂贵的微生物处理替代了长期的成熟期。
本发明涉及制备鸢尾酮的新方法。尤其是,本发明涉及用亚硝酸盐的水溶液对鸢尾根状茎、这种根状茎的部分、鸢尾提取物、鸢尾提取物的废物、或者其它任何含有鸢尾酮前体的鸢尾植物组织以及它们的混合物进行处理,以释放,即形成、产生鸢尾酮,并回收所形成的鸢尾酮的方法。所谓的鸢尾酮应理解为是由γ-鸢尾酮、顺-α-鸢尾酮、反-α-鸢尾酮及β-鸢尾酮组成的异构体混合物,这种情况是鸢尾根状茎提取物中常见的。所谓的鸢尾酮前体应理解为当用亚硝酸盐处理时能产生鸢尾酮的化合物或由这些化合物组成的混合物。优选那些具有高含量的鸢尾酮前体的鸢尾种类。
出乎意料的是,现在发现以亚硝酸盐水溶液在适温下处理根状茎,即新鲜的鸢尾根状茎粉末可释放,即形成鸢尾酮,在温和的条件下有出色的产率。所得鸢尾酮中的异构体和对映体的分布与传统的成熟法所得的是一致的。
可用不同的阳离子与亚硝酸根阴离子进行组合。阳离子用碱金属、碱土金属或铵类,即用亚硝酸钠、亚硝酸钾、亚硝酸钙、亚硝酸铵等时可得到很好的结果,优选使用亚硝酸钠或亚硝酸钾。亚硝酸盐(nitrite)的适当的浓度从约0.1克/升到约5克/升,优选约0.5到约1克/升。
鸢尾根状茎提取物与媒介物即水溶液的适当的重量比的范围从约1∶20到约2∶1,优选约1∶5到约1∶20。
亚硝酸盐处理的适当的pH范围从1到约6,更优选从约2到约5。优选的pH在约2到约3之间。
可使用适当的酸,例如H3PO4或其它无机酸用于调节所需的pH值。
在温和温度下处理是有效的。在约10到50℃之间得到最好的效果,优选室温,例如在20到30℃之间。
完成产生鸢尾酮所需的时间取决于处理的条件。本方法中适宜的反应时间从约1小时到5天(120小时),优选约5到36个小时。
对新收获的Iris Pallida的根状茎的处理用初始鸢尾酮含量为12毫克/千克干根状茎在室温25℃,pH2.5以100克/升悬浮于0.1%的亚硝酸钠溶液中,30小时后释放的产品范围为1200-1400毫克鸢尾酮/千克干根状茎。
鸢尾属(Iridacea科)的根状茎、部分这种根状茎、鸢尾废物或提取物以及更常规地所有含鸢尾酮前体的植物组织都可使用。本发明的根状茎底物优选来自于选自下列的鸢尾植物:I.Pallida、德国鸢尾、I.florentina、Iris of Verona以及它们的混合物,优选I.pallida。
鸢尾底物优选从处于营养状态即生长期的植株中获取,它可以以下列形式在新鲜状态或收获后很短时间使用:
鸢尾根状茎,即碎裂的或粉状的,
鸢尾根状茎部分及鸢尾根状茎提取物,即用任何有机溶剂溶解该鸢尾酮前体所得的提取物,优选醇即链烷醇,更优选甲醇提取物,
鸢尾废物,即鸢尾根状茎工业提取后回收的残余物,
鸢尾植物细胞培养物,如EP 0353683所述,
或其混合物。
通过目前使用的传统的方法可以方便地进行终产物的提取,这些方法常用于从植物中分离挥发物,例如用于生产芳香剂或矫味剂,即水馏(hydrodistillation)(蒸汽蒸馏)或用任何适当的挥发性有机溶剂,即乙醇、己烷及其混合物进行提取。根据根状茎的质量,通过优选方法即水馏方法所得的鸢尾脂含例如15-30%的鸢尾酮。
出乎意料地发现在许多来源各异的鸢尾纯系,例如Iris Pallida及德国鸢尾中,目前所发现的一个重要差异就是关于鸢尾酮前体的含量(Jehan等,C.R.Acad.Sci.Paris,Sciences de la vie/Life science,1994;
317:424-429)。因此,对56株不同植物(I.Palida)应用上述的成熟法时,处理后表明鸢尾酮含量范围在约1100-约1800毫克鸢尾酮/千克干根根状茎之间。已经发现有几个纯系其鸢尾酮含量要比常规的商业I.Pallidas的含量超出50%-65%。因此本发明还涉及对选择的纯系如GRN1纯系、GRN2纯系等使用新的成熟方法,其特征是在生产鸢尾提取物时鸢尾酮前体的高含量。
因此本方法是建立在已确定的56个Iris Pallida纯系的纯粹的田间选择的基础之上的。通过Jehan等所述的方法以微生物处理来实现对鸢尾酮含量的评估。增殖、微繁及培养都用已知技术实现。
通过下述实施例对本发明进一步进行描述,这些实施例并不用于限制权利要求的有效范围。
实施例1
通过处理Iris Pallida根状茎生产鸢尾酮
首先从新鲜的根状茎上在Warring Blender中清除过量的土,并碾磨。在含5克亚硝酸钠的5升水溶液中,在装有机械搅拌器的反应罐里加入碾磨后的新鲜鸢尾根状茎(Iris Pallida,500克,起始鸢尾酮含量:12毫克鸢尾酮/千克干根状茎)。在以5摩尔/升H3PO4把pH调至2.5后,室温下将混合物温和搅拌48小时。
为了在“成熟”后测定反应混合物中鸢尾酮的含量,将50毫升反应混合物与20毫升1摩尔/升的氢氧化钠混合,并在内标物(茴香醚)存在下以80/20体积/体积的MTBE(甲基-叔-丁基醚)和乙醇的混合物进行提取。通过GC分析离心后的有机层;GC:Carbowax 20M柱,30米,直径0.32毫米,升温程序:60℃4分,12℃/分直到150℃,3℃/分直到240℃。成熟悬浮液含1840毫克鸢尾酮/千克干根状茎。所得成熟混合物在装有短径柱(short pathcolumn)、进行全蒸馏的浓缩器(相分离器)和用于水相循环的装置的蒸馏仪中水馏所得的成熟混合物。所得鸢尾脂(1.85克,产率0.37%/新鲜根状茎或0.92%干根状茎)于回收器表面回收。鸢尾脂的GC分析在有内标物存在下以下述方法进行:即约50毫克鸢尾脂被精确称量后置入50毫升瓶中,在加入内标物及5毫升1摩尔/升的氢氧化钠(Sodium hydroxyde)溶液后,将不均匀的混合物强烈搅拌15分钟;5ml所得上层相与1毫升甲醇混合后如上述进行GC分析。所得鸢尾脂的鸢尾酮含量为16.2%。
实施例2
从选自具有高含量鸢尾酮前体的Iris Pallida的根状茎的处理生产鸢尾酮
用于两种类型的Iris Pallida根状茎进行实验:第一批:将来自于处于营养状态的56株不同植物(3年)的新鲜根状茎除去余土。将每份植株样本三等分(3×5克)切成碎片并于Warring Blender中研磨。然后把根状茎放入Erlenmeyer瓶(每瓶中在pH2.5下于50毫升1克/升NaNO2水溶液加入8克)。这三个瓶子被置于一个回转摇动器(100转/分)上25℃24小时。对照实验以与上述相同的方法进行只是不用NaNO2溶液。
24小时处理结束之后,根状茎和液相都用MTBE提取,可一块进行或分别进行,(即可把根状茎部分通过过滤或离心而分离)。混合提取物(从根状茎和液相同提取)以实施例1中所述以气相色谱(GC)分析。
第二批:从培育3年后不同来源的56株纯系,以“C.R.Acad.Sci.Paris.Sciences de la vie/Life Science,(317)424-429(1994)”所述的方法因其生长和高含量的鸢尾酮前体而选出的两株纯系(GRN1和GRN2)。新鲜鸢尾酮处理如上(第一批)。结果(以每千克干重鸢尾根状茎中鸢尾酮的毫克数来表示)如表1所示。标准差相当于田间的三个重复。
如现在所表明的,对照样品(无任何处理的新鲜收割的根状茎)的鸢尾酮含量非常低(少于100毫克/千克干重)。
表1
第一批(*) | 第二批(GRN1) | 第二批(GRN2) | |
以NaNO2处理 | 1399(±208)(*)指不同来 | 1716(±115) | 1659(±134) |
源的56个Iris Pallida纯系 |
实施例3
通过处理Iris Pallida根状茎提取物生产鸢尾酮
在Warring Blender中研磨50克新鲜材料以得到鸢尾根状茎的粗提物(第一批,见实施例1),然后用在搅拌下1小时内用250毫升CHCl3/MeOH(1/2)进行三次提取。过滤后,浓缩混合后的成分。所得粗提物溶于10毫升MeOH中。溶液加到25℃、pH2.5的NaNO2溶液(500毫升,1克/升)中,搅拌(100转每分)24小时。总溶液如实施例1中所描述的进行提取和分析。新鲜根状茎的等分试样(在提取之前)以与实施例1相同的方法处理。结果(以每千克鸢尾根状茎干重中鸢尾酮的毫克数表示)列于表2。
表2
新鲜根状茎(提取之前) | 提取物 | |
以NaNO2处理 | 1025(+-130) | 1266(+-25) |
Claims (18)
1.一种制备鸢尾酮的方法,包括用亚硝酸盐的水溶液对鸢尾根状茎、这种根状茎的部分、鸢尾提取物、鸢尾提取物的废物或其它任何含有鸢尾酮前体的鸢尾植物组织及其混合物进行处理,以及回收所形成的鸢尾酮。
2.根据权利要求1的方法,其中鸢尾根状茎底物来自于选自下列的鸢尾植物:Iris pallida、德国鸢尾、Iris florentina、Iris of Verona及其混合。
3.根据权利要求1或2的方法,其中根状茎根据其高含量的鸢尾酮前体进行选择。
4.根据权利要求3的方法,其中根状茎是Iris pallida的纯系。
5.根据权利要求3的方法,其中根状茎是GRN 1和GRN 2的纯系。
6.根据权利要求1或2的方法,其中反应介质是亚硝酸盐的水溶液。
7.根据权利要求1的方法,其中亚硝酸盐是亚硝酸碱金属盐、碱土金属盐或铵盐。
8.根据权利要求1的方法,其中鸢尾根状茎底物是新鲜的,即未成熟的。
9.根据权利要求1的方法,其中制备了γ-鸢尾酮、顺-α-鸢尾酮、反-α-鸢尾酮和/或β-鸢尾酮。
10.根据权利要求1的方法,其中该方法在室温下进行。
11.根据权利要求10的方法,其中该方法是在20℃到30℃之间进行。
12.根据权利要求1的方法,其中该方法进行1到120小时。
13.根据权利要求12的方法,其中该方法进行5到36小时。
14.根据权利要求5的方法,其中亚硝酸盐的浓度为0.1到5克/升反应介质。
15.根据权利要求1的方法,其中该方法在1到6的pH范围内进行。
16.根据权利要求15的方法,其中该方法在2到5的pH范围内进行。
17.根据权利要求1的方法,其中鸢尾根状茎提取物与介质的重量比例范围在1∶20到2∶1之间。
18.根据权利要求1的方法,其中鸢尾酮通过提取或蒸馏而分离。
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