CN1208041A - 抗坏血酸衍生物 - Google Patents
抗坏血酸衍生物 Download PDFInfo
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- 125000003289 ascorbyl group Chemical class [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 0.000 title 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 17
- 230000032050 esterification Effects 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 12
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 9
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 claims 1
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- 241001465754 Metazoa Species 0.000 abstract description 4
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- 235000019832 sodium triphosphate Nutrition 0.000 description 10
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- 241000252233 Cyprinus carpio Species 0.000 description 5
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- 238000000034 method Methods 0.000 description 4
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
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- 229940000488 arsenic acid Drugs 0.000 description 1
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 229940088597 hormone Drugs 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 238000005805 hydroxylation reaction Methods 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
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- 239000011664 nicotinic acid Substances 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 239000001205 polyphosphate Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
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- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 108060007951 sulfatase Proteins 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/94—Bismuth compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/66—Arsenic compounds
- C07F9/70—Organo-arsenic compounds
- C07F9/80—Heterocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/90—Antimony compounds
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract
本发明是一种抗坏血酸衍生物,是为了解决抗坏血酸稳定性差,功能基少,和C2上酯化破坏了C1和C2构成的缔合环降低了抗坏血酸的稳定性和活性问题,其特点是在C3上酯化,引入了磷、砷、锑、铋含氧酸基团,从而改善了抗坏血酸物化性能,提高了其对水、热和光的综合稳定性和生物活性,开辟了抗坏血酸在养殖业、食品工业和动植物病害防治的新途径。
Description
本发明涉及到精细化工添加剂，主要用于饲料、食品，作为维生素C源及消毒杀菌的抗坏血酸衍生物，该衍生物以抗坏血酸为母体。
抗坏血酸即维生素C是动物最重要的维生素之一。它参与胶原蛋白、神经介质、激素和类固醇的羟化反应，以及氧化还原反应，具有十分重要的生物效用。但它易被氧化和水解，从而丧失其生物活性；人类、水产动物自身不能合成，仅靠外源补充，进一步加剧了维生素C的缺乏症。寻求稳定的维生素C源是科学家们长期的奋斗目标。采用包膜处理和合成其衍生物是两条主要途经。包膜处理的稳定作用效果甚微。合成衍生物最有代表性的工作是酯化，而抗坏血酸含有四个羟基，均可酯化，如在C5,C5进行酯化，不能克服抗坏血酸稳定性差的缺点。目前有L-抗坏血酸2-硫酸酯，这一化合物因机体缺乏硫酸酶，基本上不被吸收利用，不是一种好形式。L-抗坏血酸2-磷酸酯是一种较好的形式，稳定性和吸收利用都比较好，尤其是美国专利US-4,547,672提供了一种新的维生素C源L-抗坏血酸2-三聚磷酸酯，及其制备技术，开辟了维生素C源的新方向。按照P.A.Seib等人的发明，该化合物具有良好的热稳定性，也有较好的生物活性。进一步的研究表明，Seib的发明，抗坏血酸在C2-OH酯化破坏了与之联结的羟基和C1=O所形成的氢键结构，使抗坏血酸易于水解，具有生物活性的还原态的维生素C酯含量少，L-抗坏血酸效价很低，副产品很高，三磷酸的生物效用没能发挥。使这一发明的功用和应用大受限制。
本发明的目的在于克服背景技术的不足，设计一种不破坏二位碳上羟基与一位羰基形成缔合键的结构，在三位碳上引入含氮族元素的基团，并能提高稳定性，增加生物活性的抗坏血酸衍生物。
本发明的构思：为了实现上述目的，必须对抗坏血酸母体的二位碳上羟基进行保护，在三位碳上实现酯化反应。抗坏血酸在二位和三位碳上的羟基属于烯醇式结构，其氢原子易于解离，用质子(H+)可以保护二位碳上的羟基，质子可由无机酸或有机酸提供。在适宜的条件下，抗坏血酸三位碳上的羟基同氮族元素中的磷、砷、锑、铋所构成的含氧酸，发生酯化反应，从而得到稳定的高活性的抗坏血酸衍生物。
本发明的抗坏血酸衍生物，其化学结构式如下：
结构式中的Z代表下列磷砷锑铋含氧酸基团：
其中A表示钠、钾离子。
本发明的优点：
抗坏血酸在C3上酯化，保护了由C1和C2构成的缔合环，从而提高了抗坏血酸对水、光和热的综合稳定性和生物功能。L-抗坏血酸，在其C3上经三聚磷酸酯化后效果更为明显。例如L-抗坏血酸3-三聚磷酸酯，其综合稳定性超过L-抗坏血酸10倍以上，它的内酯难于水解，效价提高三倍多，副产物少。C3上经亚砷酸，偏亚砷酸，偏亚锑酸和偏亚铋酸酯化后，不但保留了L-抗坏血酸的还原特性和生物活性，还增加了消毒杀菌的功能，使这些功能基产生协合作用，效果倍增，开辟了抗坏血酸应用的新途径。
本发明可以按照下列实施例进行实施。
1．L-抗坏血酸3-三聚磷酸酯钠盐的合成，其结构式如下：
一个150ml玻璃反应器，内插玻璃PH电极，附有电磁搅拌器，在水浴中加热至50-55℃。称取L-抗坏血酸30g，三聚磷酸钠52g。向其中加入水50ml，氮气氛下先加入L-抗坏血酸10g，38%浓盐酸2ml，然后加三聚磷酸钠20g，与之交替加入剩余L-抗坏血酸，在PH2.5-3.2反应3小时，用1molNaOH调节PH至5.0，继续反应2小时，所得反应产物浓缩，真空干燥得到浅黄色的固体粉末。取出其中1/5产品，添适量水溶解经液相色谱柱纯化，干燥得到白色的粉末。
经紫外检测，在265nm有最大吸收。NMR谱分析，包括13C,1H和31P，红外谱和元素分析证明，该衍生物是L-抗坏血酸3-三聚磷酸酯钠盐。
元素分析结果。计算值：C6H7O6.P3O9Na4.2H2O；C:13.34,H:2.05,P:17.20,Na:17.02,L-抗坏血酸效价：32.43；
观察值：C:13.05,H:2.03,P:16.82,Na:15.67,L-抗坏血酸效价：32.11。
2．L-抗坏血酸3-三聚磷酸酯钾盐的合成
参照实施例1实施。不同的是把三聚磷酸钠和氢氧化钠替换成相应的钾盐，三聚磷酸钾总加入量63g。结构式为：
元素分析结果：
计算值：C:11.92,H:1.83,P:15.37,K:25.87；
观察值：C:11.68,H:1.80,P:14.91,K:24.58。
3．L-抗坏血酸3-亚砷酸酯合成，结构式如下：
反应装置和方法类似于实施例1，不同的是用亚砷酸替代三聚磷酸钠。亚砷酸的总加入量为18g。反应产物经提纯后进行有机波谱的综合分析证明该衍生物是L-抗坏血酸3-亚砷酸酯。
元素分析结果：
计算值：C:25.37,H:3.19,As:26.38；
观察值：C:24.86,H:3.15,As:25.59。
4．L-抗坏血酸3-偏亚砷酸酯合成
反应装置和方法类似于实施例3，区别在于用偏亚砷酸代替亚砷酸，其总加入量为15.3g。经有机波谱综合分析证明，该衍生物是L-抗坏血酸3-偏亚砷酸酯：
元素分析结果：
计算值：C:27.09,H:2.65,As:28.16；
观察值：C:26.68,H:2.57,As:27.32。
5．L-抗坏血酸3-偏亚锑酸酯合成，其结构式如下：
反应装置和方法类似于实施例1
分别称取L-抗坏血酸30g，偏亚锑酸22g，水50ml。往反应器中加水，温升65-70℃，加入乳酸3g；先加L-抗坏血酸10g，然后加偏亚锑酸，并交替加入L-抗坏血酸，PH3.5，保持2小时，用1mol氢氧化钾调节PH5.5，保持1.5小时。最后纯化，经有机波谱和元素分析证明是L-抗坏血酸3-偏亚锑酸酯。
元素分析结果：
计算值：C:23.03,H:2.25,Sb:38.92；
观察值：C:22.45,H:2.20,Sb:37.36。
6．L-抗坏血酸3-偏亚铋酸酯的合成，其结构式如下：
反应装置和方法类似于实施例5，其不同点是，用偏亚铋酸代替偏亚锑酸。偏亚铋酸的总加入量为34g。纯化后的产物，经元素分析和有机波谱检测证明是L-抗坏血酸3-偏亚铋酸酯。
元素分析结果：
计算值：C:18.01,H:1.76,Bi:52.23；
观察值：C:17.47,H:1.73,Bi:50.77。
本发明的应用，饲喂鲤鱼试验。在盛有20L水的鱼缸中放入五条0.5kg重的鲤鱼，30℃水温下饲养。设试验和对照两组，均用充气器通入空气。试验组强饲本发明L-抗坏血酸3-三聚磷酸酯，对照组分别强饲效价相同的L-抗坏血酸和L-抗坏血酸2-三聚磷酸酯(紫外最大吸收258nm)。饲喂2小时后，饲喂本发明的试验组在持续14小时内，鲤鱼呼吸频率下降20-30%，而全部对照组均无此效果，呼吸频率反而升高。表明本发明对于鲤鱼的抗缺氧抗应激性能效果显著。
此外本发明添加到鲤鱼、草鱼、对虾、鳗鱼等饵料中，增加产量和提高饲料报酬8％以上。
本发明L-抗坏血酸3-亚砷酸酯添加到对虾饵料中饲喂对虾，显著提高了对虾的健康水平和抗病能力。本发明L-抗坏血酸3-偏亚砷酸酯，L-抗坏血酸3-偏亚锑酸酯和L-抗坏血酸3-偏亚铋酸酯有促进创口愈合，抑制或杀灭病毒病菌的功用。
本发明所述的L-抗坏血酸衍生物，在三位碳上酯化，还可以是其它形式的多聚磷酸、砷酸、锑酸、铋酸，或它们的盐类，有机酸也可以是亚麻酸、柠檬酸、乳酸、烟酸、叶酸等。也可使该系列L-抗坏血酸衍生物形成相应的碱金属、碱土金属盐。
本发明L-抗坏血酸3-多聚磷酸酯作为一种新型的维生素C源，已在水产养殖中应用。本发明开辟了抗坏血酸在养殖业、食品工业和动植物病害防治的新途径。
Claims (1)
1．一种抗坏血酸衍生物，其特征在于在抗坏血酸O3上酯化，引入磷、砷、锑和铋含氧酸基团，其结构式如下：
结构式中Z代表：
-SbO和-BiO，其中A表示Na+和K+。
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| CN95118385A CN1208041A (zh) | 1995-11-28 | 1995-11-28 | 抗坏血酸衍生物 |
| PCT/CN1996/000105 WO1997019949A1 (fr) | 1995-11-28 | 1996-11-27 | Derives d'acide ascorbique et leur preparation |
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| CN105330701A (zh) * | 2015-11-27 | 2016-02-17 | 昆明医科大学 | 一种含砷化合物及其制备方法和应用 |
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| US10150792B2 (en) * | 2010-11-08 | 2018-12-11 | Synthonics, Inc. | Bismuth-containing compounds, coordination polymers, methods for modulating pharmacokinetic properties of biologically active agents, and methods for treating patients |
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| CN105330701A (zh) * | 2015-11-27 | 2016-02-17 | 昆明医科大学 | 一种含砷化合物及其制备方法和应用 |
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