新型稳定维生素C源的合成研究
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摘要
VC又叫 抗坏血酸。是一种具有连二烯醇结构的五元环内酯，易受到光、热、氧、湿气、pH和金属离子等的影响。基于VC的易于氧化和对热不稳定，寻求稳定VC源势在必行。本论文研究了两种新型稳定VC源—VC多聚磷酸酯（AsPP）与VC棕榈酸酯（AP）的制备，并研究了VC多聚磷酸酯的稳定性。
本论文采用两种不同的磷酸化试剂与维生素C反应合成了VC多聚磷酸酯。（1）采用六偏磷酸钠作为磷酸化试剂，单因素试验方法合成了VC多聚磷酸酯。（2）采用三偏磷酸钠作为磷酸化试剂，用正交法合成了VC多聚磷酸酯。该方法的最佳合成工艺条件为pH=10.00、n（L-抗坏血酸）：n（三偏磷酸钠）=1.00：1.30、反应温度为t=34℃、不使用催化剂。所得产品经IR、13C—NMR分析证明其结构与预期产物相符。AsPP在碱性条件下较在酸性条件下稳定，在pH=10.00的碳酸盐缓冲溶液中最为稳定。
采用两种方法合成了VC棕榈酸酯。（1）以L—抗坏血酸与棕榈酸为基本原料，以高浓度硫酸为催化剂，棕榈酸甲酯为中间体，利用酯交换法在L—抗坏血酸的C6—OH上酯化合成了VC棕榈酸酯。产率为84.4%。（2）以L—抗坏血酸与棕榈酸为基本原料，棕榈酰氯为中间产物，以酰氯法合成了VC棕榈酸酯。产率72.5%。产品经元素分析、IR、C—NMR分析证明其结构与预期相符。
Vitamin C is also called as ascorbic acid,which is a cyclopent-ester,with a hydroxy group in each carbon atom of the carbon-carbon double bond.For its special structure,it is easily affected by light、heat、oxygen、huminity、pH and metal cations.For its easily to be oxidated,unstable to heat ,it is urgent to develop new vitamin C source.In this article we have studied two kinds of new stable vitamin Cs synthesis,they are ascorbyl polyphosphate(AsPP)and ascorbyl palmitate(AP).We have also studied the stability of ascorbyl polyphosphate.
In this article,we used two kinds of phosphate agent to react with vitamin C to prepare ascorbyl polyphosphate.(1)We used sodium hexmetaphosphate as phosphate agent,using single -factor experimental method,successfully synthesized the expected product.(2)Using sodium trimetaphosphate as phosphate agent ,we used orthogal design to seek the best synthetic methodology of ascorbyl polyphosphate.When the molar ratio of L-ascorbic acid and sodium trimetaphosphate was 1.00:1.30,pH=10.00,the temperature of the solution was 34℃,with no catalyst ,we got a high yield 99.8% and with high quality.The structure of the product has been confirmed by IR and C-NMR.
In this article,we used two different methods to synthesis ascorbyl palmitate.(1)ester-exchange method.First,palmitic acid was esterified and methyl palmitate was obtained.Then ascorbyl palmitate was prepared through methyl palmitate with ascorbic acid at the presence of high concentrated sulfic acid.(2)Acyl esterific method.First,palmitic acid was acylated and palmitoyl chrolide was obtained.Then ,L-ascorbyl palmitate was prepared through palmitoyl chrolide reating with L-ascorbic acid.The IR and C-NMR spectra of the product was identified.
本论文采用两种不同的磷酸化试剂与维生素C反应合成了VC多聚磷酸酯。（1）采用六偏磷酸钠作为磷酸化试剂，单因素试验方法合成了VC多聚磷酸酯。（2）采用三偏磷酸钠作为磷酸化试剂，用正交法合成了VC多聚磷酸酯。该方法的最佳合成工艺条件为pH=10.00、n（L-抗坏血酸）：n（三偏磷酸钠）=1.00：1.30、反应温度为t=34℃、不使用催化剂。所得产品经IR、13C—NMR分析证明其结构与预期产物相符。AsPP在碱性条件下较在酸性条件下稳定，在pH=10.00的碳酸盐缓冲溶液中最为稳定。
采用两种方法合成了VC棕榈酸酯。（1）以L—抗坏血酸与棕榈酸为基本原料，以高浓度硫酸为催化剂，棕榈酸甲酯为中间体，利用酯交换法在L—抗坏血酸的C6—OH上酯化合成了VC棕榈酸酯。产率为84.4%。（2）以L—抗坏血酸与棕榈酸为基本原料，棕榈酰氯为中间产物，以酰氯法合成了VC棕榈酸酯。产率72.5%。产品经元素分析、IR、C—NMR分析证明其结构与预期相符。
Vitamin C is also called as ascorbic acid,which is a cyclopent-ester,with a hydroxy group in each carbon atom of the carbon-carbon double bond.For its special structure,it is easily affected by light、heat、oxygen、huminity、pH and metal cations.For its easily to be oxidated,unstable to heat ,it is urgent to develop new vitamin C source.In this article we have studied two kinds of new stable vitamin Cs synthesis,they are ascorbyl polyphosphate(AsPP)and ascorbyl palmitate(AP).We have also studied the stability of ascorbyl polyphosphate.
In this article,we used two kinds of phosphate agent to react with vitamin C to prepare ascorbyl polyphosphate.(1)We used sodium hexmetaphosphate as phosphate agent,using single -factor experimental method,successfully synthesized the expected product.(2)Using sodium trimetaphosphate as phosphate agent ,we used orthogal design to seek the best synthetic methodology of ascorbyl polyphosphate.When the molar ratio of L-ascorbic acid and sodium trimetaphosphate was 1.00:1.30,pH=10.00,the temperature of the solution was 34℃,with no catalyst ,we got a high yield 99.8% and with high quality.The structure of the product has been confirmed by IR and C-NMR.
In this article,we used two different methods to synthesis ascorbyl palmitate.(1)ester-exchange method.First,palmitic acid was esterified and methyl palmitate was obtained.Then ascorbyl palmitate was prepared through methyl palmitate with ascorbic acid at the presence of high concentrated sulfic acid.(2)Acyl esterific method.First,palmitic acid was acylated and palmitoyl chrolide was obtained.Then ,L-ascorbyl palmitate was prepared through palmitoyl chrolide reating with L-ascorbic acid.The IR and C-NMR spectra of the product was identified.
引文
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[3]冯国忠、马爱霞、孙祺 维生素C的产销现状分析及前景探讨 上海医药1997，2
[4]陶剑虹 维生素C系列产品开发概况及发展趋势 化学医药工业信息1997，13（1）
[5]李健、万宇、储怀付 新型稳定VC源 L-抗坏血酸-2-三聚磷酸酯（AsPP） 粮食与饲料工业 1997，2.29-30
[6]罗微素安定C-一种应用于水产中的微生素C 饲料工业1996，17（7）
[7]徐积恩 维生素C 衍生物的开发和应用.食品饲料添加剂信息.1999，8.1-3
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[24]Sandnes,K.,Torrissen,O.,Waagbo,R.,1992.The minium dietary requirement of vitamin C in Atlantic salmon Salmo salar fry using Ca ascorbate
-2-monophosphate as dietary source.Fish Physiol.Biochem. 10,315-319.
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[31]张景宏、士亚青、盛福全 VC三聚磷酸酯的开发应用 中国饲料 1995.13.11-13
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[34]Richard L Koch ，Paul A Seb， Carl hoseney。Incorpanating Ascorbyl 6-Palmitate in Bread and Its Shorening-Sparing and Anti-firing Effects。Journal of Food Science，1987，52（4），954-957
[35]Nrisinha P Sen ，et al。Inhibition of Nitrosamine ine Formation in Fried Bacon by Propyl Gallate and L-Ascorbyl Palmitate。J Agric Food Chem，1976，24（2），397-401
[36]Paul.A.Seib；Ming-Long Liao Ascorbate 2-polyphosphate esters and method of making the same[P]US：4647672
2>
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[40]Paul.A.Seib；Xiao Y.Wang Method of preparing 2-phosphorylated compound of ascorbic acid[P]US：5110950
[41]张越、李小云、侯钰、翟学良 L-抗坏血酸-2聚磷酸酯的合成 精细化工，2000，5.263-264
[42]张志诚、任培桃 L-抗坏血酸-2-三聚磷酸酯的合成、稳定性及饲喂效果的研究.饲料研究.1999.4.12-13
[43]李正化.药物化学（第二版），北京人民卫生出版社，1985.394
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[45]天津轻工学院食品教研室编.食品添加剂（修订本）.北京轻工业出版社，1985，71
[46]罗清波.医药情报，1993，（3）：53-57
[47]美国专利：US PS2350435
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[52]北原文雄等编，孙绍曾等译.表面活性剂.北京：化学工业出版社，1984：47-5
[53]张铸勇主编.精细有机合成单元反应.上海：华东化工学院出版社，1990：272
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[2] 吴水清 抗坏血酸在电镀度工业中的应用.电镀与精饰.1995.1.21-24
[3]冯国忠、马爱霞、孙祺 维生素C的产销现状分析及前景探讨 上海医药1997，2
[4]陶剑虹 维生素C系列产品开发概况及发展趋势 化学医药工业信息1997，13（1）
[5]李健、万宇、储怀付 新型稳定VC源 L-抗坏血酸-2-三聚磷酸酯（AsPP） 粮食与饲料工业 1997，2.29-30
[6]罗微素安定C-一种应用于水产中的微生素C 饲料工业1996，17（7）
[7]徐积恩 维生素C 衍生物的开发和应用.食品饲料添加剂信息.1999，8.1-3
[8]蔡力创、吕积国、高立贞、张学琴L-抗坏血酸-6棕榈酸酯的合成研究 江西科学1999，9
[9]Alami,Durante,H.,Charlon,N.,Escaffre,A.M.Bergot,P.,1991.Supplementation of artificial diets for common carp(Cyprinus carpio L.).93,167-175
[10]Boonyaratpalin,m.,Boonyaratpalin,S.,Supamataya,K.,1992.Ascorbyl-phosphate-Mg as dietary vitamin C source for seabass(Lates calcarifer).In the proceedings of the Third Asian Fisheries Forum,Singapore,26-30October 1992,PP.1-18
[11]Bouirgeois,C.F.,Chartois,H.R.,Coustans,M.F.,George,P.R.,1989.Dosage automatise de la vitamin C dans les aliments et les milieux biologiques.Analysis9,519-525.
[12]Charlon,N.,Bergot,P.,1984.Rearing system for feeding fish larvae on dry diets.Trial with carp (Cyprinus carpio L.)larvae.Aquaculture41,1-9.
[13]Chavez de Martinez,M.Ch.,1990.Vitamin C requirement of the Mexican native cichlid Cichlasoma urophthalmus(Gunther).Aquaculture86,409-41
6.
[14]Dabrowski,K.,1990.Ascorbic acid status in the early life of whitefish (Coregonus lavaretus).Aquaculture84,61-70.
[15]Dabrowski,K.,Hinterleitner,S.,Sturmbauer,C.,El-Fiky,N.,Wieser,W.,1988.Do carp larvae require vitamin C?.Aquaculture72,295-306.
[16]Dabrowski,K.,Moreau,R.,El-Saidy,D.,1996.Ontogenetic sensitivity of channel catfish to ascorbic acid deficiency.J.Aquatic Anim.Health 8,22-27.
[17]Halver,J.E.,1982.The vitamins required for cultivated salmonids.Comp.Biochem.Physiol.73B,43-50.
[18]Hilton,J.W.,Cho,C.Y.,Slinger,S.J.,1987.Effects of graded levels of supplemental ascorbic acid in practical diets to rainbow trout(Salmo gairdner).J.Fish.Res.Board Cav.35,431-436.
[19]Mahajan,C.,Agrawal,N.K.,1980,Nutritional requirement of ascorbic acid by Indian major carp,Cirrhina mrigala,during early growth.Aquaculture 19,37-48.
[20]Matusiewicz,M.,Dabrowski,K.,1995 Characterization of ascorbyl esters hydrolysis in fish.Comp.Biochem.physiol.110B,739-745.
[21]Merchie,G.,Lavens,P.,Storch,V.,Ubel,U.,Nelis,H.,Deleenheer,A.,Sorgeloons,P.,1996.Influence of dietary vitamin C dosage on turbot (Scophthalmus maximus)and European sea bass (Dicentrarchua labrax)nursery stages.Comp.Biochem.Physiol.114A,123-133.
[22]Mustin,W.G.,Lovell,R.T.,1992.Na-L-ascorbyl-2-monophosphate as a source of vitamin C for channel catfish.Aquaculture 105,95-100.
[23]Sandnes,K.,1991.Vitamin C in fish nutrition-a review.Fisk.Dir.Skr.,Ser.Ernaering 5,3-32.
[24]Sandnes,K.,Torrissen,O.,Waagbo,R.,1992.The minium dietary requirement of vitamin C in Atlantic salmon Salmo salar fry using Ca ascorbate
-2-monophosphate as dietary source.Fish Physiol.Biochem. 10,315-319.
[25]Sato,M.,Yoshinaka,R.,Yamamoto,Y.,Ikeda,S.,1978.nON-essentiality of ascorbic acid in the diet of carp.Bull.Jpn.Soc.Sci.Fish.44,1151-1156.
[26]Phate for tilapia, Oreochromis niloticusv*O.aureus.Aquaulture 133,147-157.
[27]Woodward,B.,1994.Dietary vitamin requirements of cultured young fish,with emphasis on quantitative estimates for salmonids.Aquaculture 124,133-168.
[28]耿志明，L-抗坏血酸棕榈酸酯特性和应用。江苏食品与发酵。1997，7（1）；10-14
[29]陆豫，甘利军，陈葆仁。L-抗坏血酸棕榈酸酯的合成。精细化工，1996，13（3）：17-18
[30]Kokai Tokkyo KohoJP05207887[93207887]（cl，cl2P17/04），1993-08-20
[31]张景宏、士亚青、盛福全 VC三聚磷酸酯的开发应用 中国饲料 1995.13.11-13
[32]Kaymond C Cousins，et al。Synthesis of 6-Fatty Acid Esters of L-Adcoubie Acid。JAOCS，1977，54（8）：308-312
[33]Gwo Y Y，et al。Effect of Ascorbyl Palmitate on the Quality of Deep Frying Operations。JAOCS，1985，62（12）：1666-1670
[34]Richard L Koch ，Paul A Seb， Carl hoseney。Incorpanating Ascorbyl 6-Palmitate in Bread and Its Shorening-Sparing and Anti-firing Effects。Journal of Food Science，1987，52（4），954-957
[35]Nrisinha P Sen ，et al。Inhibition of Nitrosamine ine Formation in Fried Bacon by Propyl Gallate and L-Ascorbyl Palmitate。J Agric Food Chem，1976，24（2），397-401
[36]Paul.A.Seib；Ming-Long Liao Ascorbate 2-polyphosphate esters and method of making the same[P]US：4647672
[37]李摈榔。天然食用抗氧化物的研究。食品与发酵工业。1992，（4）；74-83
[38]谷利伟，翁新楚。食用天然抗氧化剂研究进展。中国油脂。1997，22（3）；37-40
[39]Dziezak JD.Antioxidants.Food Technology。1984，40（9）；94-102
[40]Paul.A.Seib；Xiao Y.Wang Method of preparing 2-phosphorylated compound of ascorbic acid[P]US：5110950
[41]张越、李小云、侯钰、翟学良 L-抗坏血酸-2聚磷酸酯的合成 精细化工，2000，5.263-264
[42]张志诚、任培桃 L-抗坏血酸-2-三聚磷酸酯的合成、稳定性及饲喂效果的研究.饲料研究.1999.4.12-13
[43]李正化.药物化学（第二版），北京人民卫生出版社，1985.394
[44]赵儒铭、周强.宜大学报，1994，8（2）4-7
[45]天津轻工学院食品教研室编.食品添加剂（修订本）.北京轻工业出版社，1985，71
[46]罗清波.医药情报，1993，（3）：53-57
[47]美国专利：US PS2350435
[48]Feather，L.R。， et al. Adv in Carbohydrate Chem. New York：McGraw Hill，1973，（28）：68
[49]Scott V 了et al.Analytical Biochemistry，1967，21：68
[50]西德专利：DE-OS 2743526
[51]陈金龙主编.精细有机原理与工艺.北京：中国轻工业出版社，1992：180
[52]北原文雄等编，孙绍曾等译.表面活性剂.北京：化学工业出版社，1984：47-5
[53]张铸勇主编.精细有机合成单元反应.上海：华东化工学院出版社，1990：272
[54]西德专利（登记号）841023658
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