CN108525664A - 一种磁性纳米核壳催化剂的制备及其应用 - Google Patents
一种磁性纳米核壳催化剂的制备及其应用 Download PDFInfo
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- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/23—
-
- B01J35/33—
-
- B01J35/397—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
- C07H15/10—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical containing unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/18—Acyclic radicals, substituted by carbocyclic rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
本发明公开了一种磁性纳米核壳催化剂的制备及其应用,其特点以提取荷叶中的多糖为碳源,将其负载在Fe3O4上,得到具有磁性的纳米核壳材料为Fe3O4@C,将其浸入FeCl3的CH2Cl2溶液中,经洗涤、干燥得Fe3O4@C@Fe3 +催化剂,该催化剂用于3,4,6‑三‑O‑乙酰基‑D‑葡糖烯与2‑卤代(Cl、Br,I)3,4,6‑三‑O‑乙酰基‑D‑葡糖烯的Ferrier重排反应,催化合成4,6‑二乙酰基2,3‑不饱和糖苷。本发明与现有技术相比具有工艺简单,生产成本低,产率高,反应条件更温和催化效率高,并可回收循环利用,原料价廉且易得,底物适用范围广,是一种绿色环保、经济高效,易于大规模工业生产。
Description
技术领域
本发明涉及核壳型分子筛技术领域,具体地说是一种磁性纳米核壳催化剂的制备及其应用。
背景技术
由Ferrier重排反应得到的2,3-不饱和糖苷在糖化学中具有重要的应用,首先作为各种手性中间体,可以用来合成一系列具有生物活性的化合物,如:糖肽和低聚糖等。其次,2,3-不饱和糖苷还可以用来合成一些重要的抗生素,核苷、糖醛酸、天然产物和修饰糖衍生物。此外,2,3-不饱和糖苷在转换成其它糖类化合物中起着重要的作用,比如可以对糖环的双键进行羟基化、加氢、氧化以及氨基羟基化,因此2,3-不饱和糖苷具有非常重要的地位。
目前,对3,4,6-三-O-乙酰基-D-葡糖烯进行Ferrier重排反应的研究很多,通常使用的催化剂主要有SnCl4、InCl3、Sc(OTf)3、Yb(OTf)3、Dy(OTf)3/ionicliquids、BiCl3、CeCl3·7H2O、ZnCl2、NbCl5、Er(OTf)3和La(NO3)3·6H2O等金属催化剂。使用上述催化剂虽然可以催化3,4,6-三-O-乙酰基-D-葡糖烯合成2,3-不饱和糖苷,但是存在着以下问题:(1)使用了一些贵金属催化剂,价格昂贵,不易得,生产成本高,不适合工业化生产;(2)反应条件苛刻,反应时间长,操作复杂,而且底物适用性窄;(3)催化剂不能回收利用,催化效率低,不能进行绿色化生产,不符合绿色化学发展要求。
综上所述,现有技术催化3,4,6-三-O-乙酰基-D-葡糖烯发生Ferrier重排合成4,6-二乙酰基2,3-不饱和糖苷收率低,生产成本高,催化剂易分离和回收,制备工艺复杂,不利于工业化生产及其广泛应用。
发明内容
本发明的目的是针对现有技术的不足而提供的一种磁性纳米核壳催化剂的制备及其应用,采用提取荷叶中的多糖为碳源,将其负载在具有磁性的纳米Fe3O4上,得到修饰的核壳Fe3O4@C,并将Fe3+固载到核壳上,得到Fe3O4@C@Fe(III)磁性核壳材料,该磁性核壳材料能高效、快速催化3,4,6-三-O-乙酰基葡萄糖烯和2-卤代(Cl、Br,I)的3,4,6-三-O-乙酰基葡萄糖烯的Ferrier重排反应,反应条件温和,反应时间短,产率可达81%-95%,催化剂可回收循环利用,生产成本低,合成方法简单,原料价廉且易得,底物适用范围广,是一种绿色环保,经济高效且很有应用前景的合成2位未取代或2-位卤素取代(Cl、Br,I)的4.6-二乙酰基2,3-不饱和糖苷的新方法,不污染环境,易于进行大规模工业生产。
实现本发明目的的具体技术方案是:一种磁性纳米核壳催化剂的制备,其特点以提取荷叶中的多糖为碳源,将其负载在Fe3O4上,得到具有磁性的纳米核壳材料为Fe3O4@C,然后将其浸入FeCl3的CH2Cl2溶液中,经洗涤、干燥得到磁性纳米核壳材料为Fe3O4@C@Fe3+催化剂,具体制备步骤如下:
a、多糖的提取
将清洗、干燥后的荷叶研磨成粉末用去离子水浸泡20~24h,然后在60~110℃温度下加热4~8小时,加热处理后的物料经减压蒸馏和真空干燥,得到荷叶的提取物为多糖。
b、Fe3O4@C的制备
将上述提取的多糖溶于PEG后加入纳米级的Fe3O4混合,在重量浓度为98%的H2SO4下进行二次碳化处理,碳化后的产物用去离子水和丙酮交替洗涤,真空干燥后得磁性纳米核壳材料为Fe3O4@C微粒;所述多糖与PEG和Fe3O4的重量体积比为1g:1~3ml;0.05~0.5g;所述碳化处理采用超声波,每次碳化时间为5~20min,每次碳化H2SO4的添加量与多糖的体积重量比为0.5~3ml:1g。
c、Fe3O4@C@Fe3+的制备
将上述制备的Fe3O4@C微粒在CH2Cl2饱和的FeCl3溶液中浸泡10~20h,浸泡处理后的物料用CH2Cl2洗涤三次,真空干燥后得磁性纳米核壳材料为Fe3O4@C@Fe3+催化剂。
一种磁性纳米核壳催化剂的应用,其特点是该磁性纳米核壳催化剂用于3,4,6-三-O-乙酰基-D-葡糖烯与2-卤代(Cl、Br,I)3,4,6-三-O-乙酰基-D-葡糖烯的Ferrier重排反应,催化合成4,6-二乙酰基2,3-不饱和糖苷,所述3,4,6-三-O-乙酰基-D-葡糖烯与2-卤代(Br,I)3,4,6-三-O-乙酰基-D-葡糖烯按1mmol:10~40ml摩尔体积比混合,搅拌下加入1.2~1.5eq(当量)的受体和0.1~1eq(当量)的Fe3O4@C@Fe3+纳米核壳催化剂进行Ferrier重排反应,其反应温度为20~80℃,反应时间为0.15~2h,反应结束后滤出的催化剂待回收利用,其滤液经浓缩提纯后得产物为4,6-二乙酰基2,3-不饱和糖苷;所述受体为苄醇、乙醇、正辛醇、异丙醇、叔丁醇、环己醇、烯丙醇、炔丙醇、三氯乙醇、5-羟甲基糠醛、胆固醇、薄荷醇、苯酚、对甲氧基苯酚、对溴苯酚、2,3,4-三-苄基-6-羟基-α吡喃葡萄糖甲苷或2,3,4-三-苄基-6-羟基-α-吡喃木糖甲苷。
本发明与现有技术相比具有良好催化活性和易于分离,工艺简单、操作方便,生产成本低,产率高,反应条件更温和,而且催化剂具有磁性,方便的回收循环利用,催化效率高,节约资源,不污染环境,能高效快速的催化3,4,6-三-O-乙酰基葡萄糖烯和2-卤代(Cl、Br,I)的3,4,6-三-O-乙酰基葡萄糖烯的Ferrier重排反应,原料价廉且易得,底物适用范围广,是一种绿色环保,经济高效且很有应用前景的合成2位未取代或2-位卤素取代(Br,I)的4.6-二乙酰基2,3-不饱和糖苷的新方法,不污染环境,易于进行大规模工业生产。
具体实施方式
本发明将2位未取代和2未卤素取代的3,4,6-三-O-乙酰基葡萄糖烯与二氯甲烷或二氯乙烷搅拌混合后加入受体,然后在磁性纳米核壳催化剂Fe3O4@C@Fe3 +催化下,温度为20~80℃,发生Ferrier重排,合成2位未取代和2-卤素(Br,I)取代的4,6-二-O-乙酰基-2,3不饱和糖苷,其反应方程式如下:
其中:PGO为乙酰基保护基团;X为H、Br或I;ROH为烷基醇、芳基醇和糖基受体。
以下将通过具体的实施例对本发明做进一步的阐述:
实施例1
a、多糖的提取
收集废荷叶,并用蒸馏水反复冲洗五次除去表面的污染物,将洗过的荷叶在60℃温度的真空干燥箱中干燥24小时,然后研磨成细粉。将5g粉末加入到150mL去离子水中并浸泡24h,然后将浸泡的混合物在80℃下加热4.5小时后减压蒸馏除去水,最后将残余物在真空干燥箱中在80℃温度下干燥完全,得到固体多糖提取物1.2g。
b、Fe3O4@C的制备
将上述荷叶中提取的1.2g固体多糖完全溶解于5mL PEG400中,再加入0.24g纳米级的Fe3O4,在超声波下超声15分钟,然后再加入3ml重量浓度为98%的H2SO4,超声10min充分碳化,得到的产物用去离子水和丙酮洗涤,并在真空干燥箱中干燥8小时,得磁性纳米核壳材料为Fe3O4@C微粒0.98克。
c、Fe3O4@C@Fe3 +的制备
将上述获得的磁性纳米核壳材料Fe3O4@C微粒在FeCl3的CH2Cl2溶液(0.4g/l)中浸泡12h,最终产物用CH2Cl2洗涤三次,除去表面多余的FeCl3,真空干燥后得磁性纳米核壳材料为Fe3O4@C@Fe3+催化剂。
上述制备的磁性纳米核壳Fe3O4@C@Fe3 +催化剂采用络合滴定的方法进行了表征,具体操作步骤如下:取20mg催化剂分散在50ml的去离子水中,充分振荡,加入0.2ml浓硫酸调节pH=2,再加入0.5ml浓度为200mg/mL的磺酸基水杨酸作为指示剂,配置浓度为0.01M的EDTA溶液作为络合剂,加热含Fe3 +的溶液温度至55℃,使用EDTA溶液进行滴定至溶液由紫色恰好转变为淡黄色,共消耗EDTA溶液2.5ml,计算得知溶液中Fe3+的含量为0.025mmol,从而可知实施例1制备的催化剂,其Fe3+的含量为1.25×10-3mmol/mg。
实施例2
取54.4mg(0.2mmol)3,4,6-三-O-乙酰基-D-葡萄糖烯溶于2ml二氯乙烷中,搅拌下加入24μL(0.24mmol)的苄醇,然后加入16mg上述制备的Fe3O4@C@Fe3+催化剂,转移到60℃温度的油浴中反应,TLC板跟踪监测反应(PE:EA=3:1),10min后TLC监测原料反应完全,反应结束后用磁铁吸出磁性催化剂,滤液经浓缩和硅胶柱层析分离(PE:EA=8:1),得到无色糖浆4,6-二-O-乙酰基-D-葡萄糖烯苄醇苷59.7mg,其重排反应的产率为94%。
对上述实施例所得产物4,6-二-O-乙酰基-D-葡萄糖烯苄醇苷进行1H-核磁谱分析,测试数据如下:
1H NMR(500MHz,CDCl3)δ7.36(d,J=4.9Hz,5H),5.90(d,J=10.4Hz,1H),5.87–5.83(m,1H),5.33(dd,J=9.4,1.3Hz,1H),5.20(s,1H),5.14(s,1H),4.88(d,J=11.8Hz,1H),4.81(d,J=11.7Hz,1H),4.70–4.63(m,1H),4.60(d,J=11.7Hz,1H),4.29(t,J=6.2Hz,1H),4.25(dd,J=11.6,5.0Hz,1H),4.18–4.14(m,1H),4.14–4.11(m,1H),2.10(s,3H),2.08(s,3H)。
实施例3
取3,4,6-三-O-乙酰基-D-葡萄糖烯54.4mg(0.1mmol)溶于4ml二氯乙烷中,搅拌下加入16.4μL的丙烯醇(0.24mmol),然后加入40mg实施例1制备的Fe3O4@C@Fe3+催化剂,转移到60℃温度的油浴中反应,TLC板跟踪监测反应(PE:EA=3:1),10min后TLC监测原料反应完全,反应结束后用磁铁吸出磁性催化剂,滤液经浓缩和硅胶柱层析分离(PE:EA=6:1),得到无色糖浆4,6-二-O-乙酰基-D-葡萄糖烯丙烯醇苷51.2mg,其重排反应的产率为95%。
对上述实施例所得产物4,6-二-O-乙酰基-D-葡萄糖烯丙烯醇苷进行1H-核磁谱分析,测试数据如下:
1H NMR(500MHz,CDCl3)δ5.98–5.90(m,1H),5.89(d,J=10.1Hz,1H),5.85–5.81(m,1H),5.33–5.27(m,2H),5.20(dd,J=10.4,1.2Hz,1H),5.07(s,1H),4.29–4.22(m,2H),4.17(dd,J=12.1,2.3Hz,1H),4.14–4.05(m,2H),2.09(s,3H),2.07(s,3H)。
实施例4
取3,4,6-三-O-乙酰基-D-葡萄糖烯54.4mg(0.1mmol)溶于4ml二氯乙烷中,搅拌下加入37.4μL的丙烯醇(0.24mmol),然后加入40mg实施例1制备的Fe3O4@C@Fe3+催化剂,转移到60℃温度的油浴中反应,TLC板跟踪监测反应(PE:EA=3:1),10min后TLC监测原料反应完全,反应结束后用磁铁吸出磁性催化剂,滤液经浓缩和硅胶柱层析分离(PE:EA=10:1),得到无色糖浆4,6-二-O-乙酰基-D-葡萄糖烯薄荷醇苷68.7mg,其重排反应的产率为94%。
对上述实施例所得产物4,6-二-O-乙酰基-D-葡萄糖薄荷醇苷进行1H-核磁谱分析,测试数据如下:
1H NMR(500MHz,CDCl3)δ5.84-5.85(m,2H),5.27(d,J=9.3Hz,1H),5.08(s,1H),4.24–4.13(m,3H),3.36-3.41(m,1H),2.15-2.17(m,1H),2.09(s,3H),2.06(s,3H),1.62–1.58(m,2H),1.40–1.37(m,1H),1.06-1.10(m,1H),1.05–0.99(m,1H),0.92-0.98(m,1H),0.90–0.86(m,6H),0.82-0.84(m,1H),0.78–0.75(m,3H)。
实施例5
将上述各实施例中回收的催化剂按下述结构反应式为模板反应,进行催化剂循环测试:
反应后Fe3O4@C@Fe3+催化剂分散在反应溶液中,通过外部磁铁收集使其聚集,然后从混合物中除去液体溶液以留下催化剂,最后,用DCM洗涤催化剂以除去吸附的产物,真空干燥并在随后的反应中重新使用,在对催化剂进行5个循环实验后,产率仍可以达到84%。
以上各实施例只是对本发明做进一步说明,并非用以限制本发明专利,凡为本发明等效实施,均应包含于本发明专利的权利要求范围之内。
Claims (2)
1.一种磁性纳米核壳催化剂的制备,其特征在于以提取荷叶中的多糖为碳源,将其负载在Fe3O4 上,得到具有磁性的纳米核壳材料为Fe3O4 @C,然后将其浸入FeCl3的CH2Cl2溶液中,经洗涤、干燥得到磁性纳米核壳材料为Fe3O4 @C @ Fe3+催化剂,具体制备步骤如下:
a、多糖的提取
将清洗、干燥后的新鲜荷叶研磨成粉末用去离子水浸泡20~24h,然后在60~110℃温度下加热4~8小时,加热处理后的物料经减压蒸馏和真空干燥,得到荷叶的提取物为多糖;
b、Fe3O4 @C的制备
将上述提取的多糖溶于PEG后加入纳米级的Fe 3 O 4混合,在重量浓度为98%的H 2 SO4下进行二次碳化处理,碳化后的产物用去离子水和丙酮交替洗涤,真空干燥后得磁性纳米核壳材料为Fe3O4 @C 微粒;所述多糖与PEG和Fe 3 O 4的重量体积比为1g:1~3ml;0.05~0.5g;所述碳化处理采用超声波,每次碳化时间为5~20min,每次碳化H 2 SO 4的添加量与多糖的体积重量比为0.5~3ml:1g;
c、Fe3O4 @C@Fe3+的制备
将上述制备的Fe3O4 @C微粒在FeCl3的CH2Cl2溶液中浸泡10~20h,浸泡处理后的物料用CH2Cl2洗涤三次,真空干燥后得磁性纳米核壳材料为Fe3O4 @C@Fe3+ 催化剂。
2.一种权利要求1所述磁性纳米核壳催化剂的应用,其特征在于该磁性纳米核壳催化剂用于3, 4, 6-三-O-乙酰基-D-葡糖烯与2-卤代(Br,I)3, 4, 6-三-O-乙酰基-D-葡糖烯的Ferrier重排反应,催化合成4,6-二乙酰基2,3-不饱和糖苷,所述3, 4, 6-三-O-乙酰基-D-葡糖烯与2-卤代(Cl、Br,I)3, 4, 6-三-O-乙酰基-D-葡糖烯按1mmol:10~40ml摩尔体积比混合,搅拌下加入1.2~1.5eq的受体和0.1~1eq的Fe3O4 @C @Fe3+ 纳米核壳催化剂进行Ferrier重排反应,其反应温度为20~80℃,反应时间为0.15~2h,反应结束后滤出的催化剂待回收利用,其滤液经浓缩提纯后得产物为4,6-二乙酰基2,3-不饱和糖苷;所述受体为苄醇、乙醇、正辛醇、异丙醇、叔丁醇、环己醇、烯丙醇、炔丙醇、三氯乙醇、5-羟甲基糠醛、胆固醇、薄荷醇、苯酚、对甲氧基苯酚、对溴苯酚、2,3,4-三-苄基-6-羟基-α吡喃葡萄糖甲苷或2,3,4-三-苄基-6-羟基-α-吡喃木糖甲苷。
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CN111632599A (zh) * | 2020-06-23 | 2020-09-08 | 华东师范大学 | 一种磁性核壳材料催化剂的制备方法及其应用 |
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