CN108456148B - N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺及其制备方法与应用 - Google Patents
N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺及其制备方法与应用 Download PDFInfo
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- -1 3,4, 5-trihydroxy benzoyl Chemical group 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- NRCGMEJBEDWPMG-UHFFFAOYSA-N 3,4,5-tris(phenylmethoxy)benzoic acid Chemical compound C=1C=CC=CC=1COC=1C(OCC=2C=CC=CC=2)=CC(C(=O)O)=CC=1OCC1=CC=CC=C1 NRCGMEJBEDWPMG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 26
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- QOURDFWPMOMRMZ-UHFFFAOYSA-N 3,4,5-trihydroxy-N-(3,4,5-trihydroxybenzoyl)benzamide Chemical compound OC=1C=C(C(=O)NC(C2=CC(=C(C(=C2)O)O)O)=O)C=C(C=1O)O QOURDFWPMOMRMZ-UHFFFAOYSA-N 0.000 claims description 13
- 150000003949 imides Chemical class 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
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- 239000000706 filtrate Substances 0.000 claims description 10
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- 238000001704 evaporation Methods 0.000 claims description 8
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
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- 238000006555 catalytic reaction Methods 0.000 claims description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims 1
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
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- XMOCLSLCDHWDHP-SWLSCSKDSA-N (+)-Epigallocatechin Natural products C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-SWLSCSKDSA-N 0.000 description 1
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 description 1
- WMBWREPUVVBILR-NQIIRXRSSA-N (-)-gallocatechin gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-NQIIRXRSSA-N 0.000 description 1
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- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
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- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 1
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- XMOCLSLCDHWDHP-IUODEOHRSA-N epi-Gallocatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-IUODEOHRSA-N 0.000 description 1
- DZYNKLUGCOSVKS-UHFFFAOYSA-N epigallocatechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3cc(O)c(O)c(O)c3 DZYNKLUGCOSVKS-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
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- A23L3/3463—Organic compounds; Microorganisms; Enzymes
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Abstract
本发明公开了一种N‑(3,4,5‑三羟基苯甲酰)‑3,4,5‑三羟基苯甲酰胺及其制备方法与应用。该化合物的结构式如(I)所示:
Description
技术领域
本发明属于具有抗氧化活性化合物的合成技术领域,具体地说,涉及一种N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺及其制备方法与应用。
背景技术
抗氧化剂是一类通过自身被氧化的方式而可以使活性氧化剂失效的化合物,广泛应用于食品、医药、饲料、化工等行业。食品在储存、加工和流通过程中,食品中的油脂类成分易受空气的氧化,发生变色或变味并会生成有害物质。添加抗氧化剂可防止食品成分氧化变质,在食品中加入抗氧化剂已成为防止食品氧化变质最经济和简单的方法。如今,合成的抗氧化剂正吸引越来越多的关注,然而对它们还没有完全开发。因此,亟需更强的抗氧化剂和自由基清除剂。随着丁基羟基茴香醚(BHA)、2,6-二叔丁基-4-甲基苯酚(BHT)、叔丁基对苯二酚(TBHQ)等抗氧化剂的副作用逐渐被研究证实,许多国家对其添加量进行了严格控制,美国、欧盟等国已禁止使用合成抗氧化剂,安全无毒的新型抗氧化剂逐渐成为研究重点。
发明内容
有鉴于此,本发明提供了一种N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺及其制备方法与应用,该化合具有良好的抗氧化活性和自由基清除能力,因此具有较高的开发应用前景。
为了解决上述技术问题,本发明公开了一种N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺,其结构式如(I)所示:
本发明还公开了一种N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺的制备方法,包括以下步骤:
步骤1、在二氯甲烷中,加入三苄基没食子酸与酰化剂进行反应,减压除去二氯甲烷和过量的二氯亚砜,制备得到酰氯;
步骤2、以四氢呋喃为溶剂,将步骤1所得酰氯与六甲基二硅胺烷按一定的摩尔比进行反应,反应液直接蒸干,乙酸乙酯结晶,制备得到酰亚胺;
步骤3、在溶剂中,将步骤2制得的酰亚胺经催化剂催化氢气还原,所得反应液用硅藻土滤过,滤液减压蒸干,残留物用乙醇重结晶,得N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺。
可选地,所述步骤1中的酰化剂为二氯亚砜或草酰氯。
可选地,所述步骤1中的反应温度为20℃~40℃,反应时间为3~5h。
可选地,所述步骤1中的酰化剂与三苄基没食子酸的质量体积比(g/mL)为159:50;三苄基没食子酸与二氯甲烷的体积比(mL/mL)为50:200。
可选地,所述步骤2中的酰氯与六甲基二硅胺烷的摩尔比为2~2.2:1。
可选地,所述步骤2中的反应温度为20℃~80℃,反应时间为1~5h。
可选地,所述步骤3中的溶剂为甲醇、乙醇或异丙醇,催化剂为10%钯碳、10%氢氧化钯碳或二氧化铂。
可选地,所述步骤3中的催化氢气还原温度为20℃~60℃,催化氢气还原时间为10~24h;酰亚胺与催化剂的质量比(g/g)为108~112:1。
本发明还公开了一种上述的N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺在制备抗氧化剂或自由基清除剂中的应用。
与现有技术相比,本发明可以获得包括以下技术效果:
1)本发明以三苄基没食子酸为原料,采用简便的合成路线实现了N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺的大批量生产,产率较高,为其在食品、化工等领域的应用提供了有力保障。
2)活性实验表明,该化合具有良好的抗氧化活性和自由基清除能力,其抗氧化活性显著强于食品行业常用的合成抗氧化剂BHT,可用于食品、化妆品和药品等领域。
当然,实施本发明的任一产品并不一定需要同时达到以上所述的所有技术效果。
具体实施方式
以下将配合实施例来详细说明本发明的实施方式,藉此对本发明如何应用技术手段来解决技术问题并达成技术功效的实现过程能充分理解并据以实施。
本发明公开了一种N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺,其特征在于,其结构式如(I)所示:
该N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺为类白色结晶性粉末,其分子式为C14H11NO8,分子量为321克/摩尔,熔点为241-243℃。该化合物是根据食品、化妆品等行业常用的抗氧化剂如:没食子酸、儿茶素、没食子儿茶素(CG)、没食子儿茶素没食子酸酯(GCG)、表没食子儿茶素没食子酸酯(EGCG)等的结构,设计合成而得到。
本发明还公开了一种N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺的制备方法,其合成路线如下:
包括以下步骤:
步骤1、在二氯甲烷中,三苄基没食子酸与酰化剂于20℃~40℃的温度下反应3~5h,减压除去二氯甲烷和过量的二氯亚砜,制备得到酰氯;
其中,酰化剂为二氯亚砜或草酰氯。酰化剂与三苄基没食子酸的质量体积比(g/mL)为159:50;三苄基没食子酸与二氯甲烷的体积比(mL/mL)为50:200。
步骤2、以四氢呋喃为溶剂,将步骤1所得酰氯与六甲基二硅胺烷按一定的摩尔比在20℃~80℃的温度下反应1~5h,反应液直接蒸干,制备得到酰亚胺;
其中,酰氯与六甲基二硅胺烷的摩尔比为2~2.2:1。
步骤3、在溶剂中,将步骤2制得的酰亚胺于20℃~60℃的温度下经催化剂催化氢气还原10~24h,所得反应液用硅藻土滤过,滤液减压蒸干,残留物用乙醇重结晶,得N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺。
其中,溶剂为甲醇、乙醇或异丙醇,催化剂为质量浓度为10%的钯碳、质量浓度为10%的氢氧化钯碳或二氧化铂。
酰亚胺与催化剂的质量比(g/g)为108~112:1。
本发明还公开了一种上述的N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺在制备抗氧化剂或自由基清除剂中的应用。
实施例1N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺的制备:
以200mL的二氯甲烷为溶剂,50mL的二氯亚砜为酰化剂加入3,4,5-三苄氧基苯甲酸(159g),20℃下反应5h,减压除去二氯甲烷和过量的二氯亚砜,残留物用300mL的四氢呋喃溶解。20℃下将六甲基二硅基氮烷(29g)缓慢滴加入上述溶液中,10min滴毕,20℃下反应5h。反应液直接蒸干后,乙酸乙酯结晶,得到白色针状结晶108g,收率69.5%,得到的产物为N-(3,4,5-三苯氧基苯甲酰)-3,4,5-三苯氧基苯甲酰胺。结构表征:熔点:188-190℃;ESI-MS m/z:862.1[M+H]+;核磁数据:1H NMR(600MHz,CDCl3,r.t.)δ:7.29-7.27(m,35H),5.20(s,4H),5.17(s,8H);13C NMR(150MHz,CDCl3,r.t.)δ:167.6,152.5,144.6,137.0,136.1,128.7,128.5,128.3,128.3,128.2,127.7,127.6,111.0,75.2,71.4。
以300mL的乙醇为溶剂,以10%的钯碳(1g)为催化剂,加入N-(3,4,5-三苯氧基苯甲酰)-3,4,5-三苯氧基苯甲酰胺(108g),20℃下氢气(一个大气压)还原,搅拌反应24h。反应液用硅藻土滤过,滤液减压蒸干,残留物用乙醇重结晶,得到类白色固体粉末33g,收率82.2%。该结晶性粉末即为最终产物N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺。结构表征:熔点:241-243℃;HRMS(ESI)calcd for C14H11NO8(M+H)+322.1426,found322.1424;核磁数据:1H NMR(600MHz,Acetone-d6,r.t.)δ:8.18(s,br,6H),7.13(s,4H),6.92(s,1H);13C NMR(150MHz,Acetone-d6,r.t.)δ:165.76,145.08,137.65,121.23,108.83。
实施例2:N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺的制备。
以200mL的二氯甲烷为溶剂,50mL的草酰氯为酰化剂加入3,4,5-三苄氧基苯甲酸(159g),40℃温度条件下加热回流反应3h,减压除去二氯甲烷和过量的草酰氯,残留物用300mL的四氢呋喃溶解。20℃下将六甲基二硅基氮烷(26.4g)缓慢滴加入上述溶液中,10min滴毕,80℃下反应1h。反应液直接蒸干后,乙酸乙酯结晶,得到白色针状结晶112g,收率72.1%,得到的产物为N-(3,4,5-三苯氧基苯甲酰)-3,4,5-三苯氧基苯甲酰胺。结构表征如实施例1所示。
以300mL的异丙醇为溶剂,以二氧化铂(1g)为催化剂,加入N-(3,4,5-三苯氧基苯甲酰)-3,4,5-三苯氧基苯甲酰胺(112g),60℃下氢气(一个大气压)还原,搅拌反应10h。反应液用硅藻土滤过,滤液减压蒸干,残留物用乙醇重结晶,得到类白色固体粉末34g,收率81.6%。该结晶性粉末即为最终产物N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺。结构表征如实施例1所示。
实施例3:N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺的制备。
以200mL的二氯甲烷为溶剂,50mL的二氯亚砜为酰化剂加入3,4,5-三苄氧基苯甲酸(159g),30℃下反应4h,减压除去二氯甲烷和过量的二氯亚砜,残留物用300mL的四氢呋喃溶解。20℃下将六甲基二硅基氮烷(29g)缓慢滴加入上述溶液中,10min滴毕,40℃下反应3.5h。反应液直接蒸干后,乙酸乙酯结晶,得到白色针状结晶109g,收率70.2%,得到的产物为N-(3,4,5-三苯氧基苯甲酰)-3,4,5-三苯氧基苯甲酰胺。
以300mL的甲醇为溶剂,以10%的氢氧化钯碳(1g)为催化剂,加入N-(3,4,5-三苯氧基苯甲酰)-3,4,5-三苯氧基苯甲酰胺(109g),40℃下氢气(一个大气压)还原,搅拌反应18h。反应液用硅藻土滤过,滤液减压蒸干,残留物用乙醇重结晶,得到类白色固体粉末35g,收率86.3%。该结晶性粉末即为最终产物N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺。结构表征如实施例1所示。
实施例4:N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺的制备。
以200mL的二氯甲烷为溶剂,50mL的草酰氯为酰化剂加入3,4,5-三苄氧基苯甲酸(159g),40℃下反应3h,减压除去二氯甲烷和过量的草酰氯,残留物用300mL的四氢呋喃溶解。20℃下将六甲基二硅基氮烷(26.4g)缓慢滴加入上述溶液中,10min滴毕,60℃下反应2h。反应液直接蒸干后,乙酸乙酯结晶,得到白色针状结晶108g,收率69.6%,得到的产物为N-(3,4,5-三苯氧基苯甲酰)-3,4,5-三苯氧基苯甲酰胺。结构表征如实施例1所示。
以300mL的异丙醇为溶剂,以10%的钯碳(1g)为催化剂,加入N-(3,4,5-三苯氧基苯甲酰)-3,4,5-三苯氧基苯甲酰胺(108g),50℃下氢气(一个大气压)还原,搅拌反应15h。反应液用硅藻土滤过,滤液减压蒸干,残留物用乙醇重结晶,得到类白色固体粉末34g,收率84.6%。该结晶性粉末即为最终产物N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺。结构表征如实施例1所示。
实施例5:N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺的制备。
以200mL的二氯甲烷为溶剂,50mL的二氯亚砜为酰化剂加入3,4,5-三苄氧基苯甲酸(159g),30℃下反应4h,减压除去二氯甲烷和过量的二氯亚砜,残留物用300mL的四氢呋喃溶解。20℃下将六甲基二硅基氮烷(29g)缓慢滴加入上述溶液中,10min滴毕,30℃下反应3h。反应液直接蒸干后,乙酸乙酯结晶,得到白色针状结晶108g,收率69.5%,得到的产物为N-(3,4,5-三苯氧基苯甲酰)-3,4,5-三苯氧基苯甲酰胺。结构表征如实施例1所示。
以300mL的甲醇为溶剂,以二氧化铂(1g)为催化剂,加入N-(3,4,5-三苯氧基苯甲酰)-3,4,5-三苯氧基苯甲酰胺(108g),30℃下氢气(一个大气压)还原,搅拌反应20h。反应液用硅藻土滤过,滤液减压蒸干,残留物用乙醇重结晶,得到类白色固体粉末34g,收率81.6%。该结晶性粉末即为最终产物N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺。结构表征如实施例1所示。
实施例6:N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺的制备。
以200mL的二氯甲烷为溶剂,50mL的草酰氯为酰化剂加入3,4,5-三苄氧基苯甲酸(159g),30℃下反应4h,减压除去二氯甲烷和过量的草酰氯,残留物用300mL的四氢呋喃溶解。20℃下将六甲基二硅基氮烷(26.4g)缓慢滴加入上述溶液中,10min滴毕,70℃下反应1.5h。反应液直接蒸干后,乙酸乙酯结晶,得到白色针状结晶109g,收率70.2%,得到的产物为N-(3,4,5-三苯氧基苯甲酰)-3,4,5-三苯氧基苯甲酰胺。结构表征如实施例1所示。
以300mL的乙醇为溶剂,以10%的氢氧化钯碳(1g)为催化剂,加入N-(3,4,5-三苯氧基苯甲酰)-3,4,5-三苯氧基苯甲酰胺(109g),30℃下氢气(一个大气压)还原,搅拌反应20h。反应液用硅藻土滤过,滤液减压蒸干,残留物用乙醇重结晶,得到类白色固体粉末35g,收率86.3%。该结晶性粉末即为最终产物N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺。结构表征如实施例1所示。
实施例7:N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺抗氧化性评价。
采用1,1-二苯基-2-三硝基苯肼(DPPH)自由基清除活性方法检测样品的抗氧化活性。
测试方法如下:样品为N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺。
将样品N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺溶于甲醇配制成合适浓度,形成样品溶液。样品管为0.l mL样品溶液+2.9mL的0.l mM DPPH甲醇溶液;对照管为0.lmL样品溶液+2.9mL甲醇;空白管为0.l mL甲醇+2.9mL的0.l mM DPPH甲醇溶液。在室温下静置30min后测定517nm处的光吸收值,以表没食子儿茶素没食子酸酯(EGCG)和BHT作为阳性对照。IC50表示清除50%DPPH自由基所需要的样品浓度。计算公式如下:
抗氧化活性结果如表1所示。结果表明,N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺的DPPH自由基清除能力显著强于食品行业常用的合成抗氧化剂BHT,其抗氧化活性也略强于EGCG。因此可以将其用于制备抗氧化剂或自由基清除剂。
表1 N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺的抗氧化活性结果
上述说明示出并描述了发明的若干优选实施例,但如前所述,应当理解发明并非局限于本文所披露的形式,不应看作是对其他实施例的排除,而可用于各种其他组合、修改和环境,并能够在本文所述发明构想范围内,通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离发明的精神和范围,则都应在发明所附权利要求的保护范围内。
Claims (10)
2.一种N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺的制备方法,其特征在于,包括以下步骤:
步骤1、在二氯甲烷中,加入三苄基没食子酸与酰化剂进行反应,减压除去二氯甲烷和过量的二氯亚砜,制备得到酰氯;
步骤2、以四氢呋喃为溶剂,将步骤1所得酰氯与六甲基二硅胺烷按一定的摩尔比进行反应,反应液直接蒸干,乙酸乙酯结晶,制备得到酰亚胺;
步骤3、在溶剂中,将步骤2制得的酰亚胺经催化剂催化氢气还原,所得反应液用硅藻土滤过,滤液减压蒸干,残留物用乙醇重结晶,得N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺。
3.根据权利要求2所述的制备方法,其特征在于,所述步骤1中的酰化剂为二氯亚砜或草酰氯。
4.根据权利要求2所述的制备方法,其特征在于,所述步骤1中的反应温度为20℃~40℃,反应时间为3~5 h。
5.根据权利要求2所述的制备方法,其特征在于,所述步骤1中的酰化剂与三苄基没食子酸的质量体积比为159 g:50 mL;三苄基没食子酸与二氯甲烷的体积比为50 mL:200 mL。
6.根据权利要求2所述的制备方法,其特征在于,所述步骤2中的酰氯与六甲基二硅胺烷的摩尔比为2~2.2:1。
7.根据权利要求2所述的制备方法,其特征在于,所述步骤2中的反应温度为20℃~80℃,反应时间为1~5 h。
8.根据权利要求2所述的制备方法,其特征在于,所述步骤3中的溶剂为甲醇、乙醇或异丙醇,催化剂为10%钯碳、10%氢氧化钯碳或二氧化铂。
9.根据权利要求2所述的制备方法,其特征在于,所述步骤3中的催化氢气还原温度为20℃~60℃,催化氢气还原时间为10~24 h;酰亚胺与催化剂的质量比为108 g ~112 g:1 g。
10.权利要求1所述的N-(3,4,5-三羟基苯甲酰)-3,4,5-三羟基苯甲酰胺在制备抗氧化剂或自由基清除剂中的应用。
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