CN108976112A - 一种乙酰丙酮银的制备方法及其作为催化剂的用途 - Google Patents

一种乙酰丙酮银的制备方法及其作为催化剂的用途 Download PDF

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CN108976112A
CN108976112A CN201810781981.6A CN201810781981A CN108976112A CN 108976112 A CN108976112 A CN 108976112A CN 201810781981 A CN201810781981 A CN 201810781981A CN 108976112 A CN108976112 A CN 108976112A
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acetylacetone
pentanedione
silver
hydrogen peroxide
preparation
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CN108976112B (zh
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于晓萍
王斌
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Yangzhou Polytechnic Institute
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/77—Preparation of chelates of aldehydes or ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/17—Silver

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Abstract

本发明涉及一种乙酰丙酮银的制备方法及其作为催化剂的用途，所述乙酰丙酮银的制备方法包括如下步骤：向硝酸银溶液中加入催化量的双氧水，室温下搅拌10‑15min后，加入乙酰丙酮、三乙胺，升温至40‑45℃反应1.5‑2小时后，过滤，滤液用氯仿稀释、水洗后，有机层(氯仿层)经减压浓缩、真空干燥即得乙酰丙酮银(Agacac)。

Description

一种乙酰丙酮银的制备方法及其作为催化剂的用途
技术领域
本发明属于配合物催化领域，具体涉及一种乙酰丙酮银的制备方法及其作为催化剂的用途。
背景技术
乙酰丙酮盐广泛用于化工、石油、医药、电子、材料等领域，主要起催化、稳定、促进等作用。例如乙酰丙酮钙是甲基丙烯酸甲酯和二甲氨基乙醇进行酯交换反应合成DMA的催化剂；乙酰丙酮铁可作为塑料光降解高效光敏催化剂；此外，乙酰丙酮钙和乙酰丙酮锌是硬质PVC等卤化物的热稳定剂，同时也是树脂硬化的促进剂。现有技术中对乙酰丙酮银(Agacac)的报道较少，本发明提供一种乙酰丙酮银的制备方法及其在催化糖苷化反应中的应用。
发明内容
本发明提供一种乙酰丙酮银的制备方法，其特征在于包括如下步骤：
向硝酸银溶液中加入催化量的双氧水，室温下搅拌10-15min后，加入乙酰丙酮、三乙胺，升温至40-45℃反应1.5-2小时后，过滤，滤液用氯仿稀释、水洗后，有机层(氯仿层)经减压浓缩、真空干燥即得乙酰丙酮银(Agacac)。
所述硝酸银溶液的浓度为0.1mol/L，双氧水选自质量分数为30％的双氧水，其用量为每升硝酸银溶液使用2mL双氧水，每毫摩尔硝酸银使用10mL乙酰丙酮、0.1mL三乙胺。
本发明的另一实施方案提供一种乙酰丙酮银(Agacac)在催化糖苷化反应中的应用。优选在催化硫苷类供体与受体发生糖苷化反应中的应用。所述硫苷类供体优选(Tol为4-甲基-苯基)，受体优选
与现有技术相比，本发明的优点在于：(1)本发明提供了一种操作简便、条件温和的制备乙酰丙酮银(Agacac)的制备方法；(2)本发明扩展了乙酰丙酮银 (Agacac)的应用，成功应用于催化硫苷类供体与受体的糖苷化反应。
具体实施方式
为了便于对本发明的进一步理解，下面提供的实施例对其做了更详细的说明。但是这些实施例仅供更好的理解发明而并非用来限定本发明的范围或实施原则，本发明的实施方式不限于以下内容。
实施例1
向硝酸银溶液(0.1mol/L，100mL)中加入30％双氧水(0.2mL)，室温下搅拌10min后，加入乙酰丙酮(100mL)、三乙胺(1mL)，升温至40℃反应2 小时后，过滤，滤液用氯仿稀释、水洗后，有机层(氯仿层)经减压浓缩、真空干燥即得乙酰丙酮银(1.99g，收率约为96.1％，紫外-可见吸收光谱与文献报道一致)。
实施例2
向硝酸银溶液(0.1mol/L，100mL)中加入30％双氧水(0.2mL)，室温下搅拌15min后，加入乙酰丙酮(100mL)、三乙胺(1mL)，升温至45℃反应1.5 小时后，过滤，滤液用氯仿稀释、水洗后，有机层(氯仿层)经减压浓缩、真空干燥即得乙酰丙酮银(1.98g，收率约为95.7％)。
实施例3
向硝酸银溶液(0.1mol/L，100mL)中加入乙酰丙酮(100mL)、三乙胺(1mL)，升温至40℃反应2小时后，过滤，滤液用氯仿稀释、水洗后，有机层(氯仿层) 经减压浓缩、真空干燥即得乙酰丙酮银(283mg，收率约为13.7％)。
实施例4
将化合物1(1.2mmol)与化合物2(1.0mmol)溶于干燥的二氯甲烷中，于 0℃下加入NIS(1.5mmol)、Agacac(0.1mmol)，保持0℃搅拌反应30min后，减压浓缩，经硅胶柱层析(200-300目硅胶，洗脱剂：石油醚/乙酸乙酯＝8:1)得化合物3(583mg，收率约为97.0％)，1HNMR(400MHz,CDCl3):δ5.64(s,1H, H-1′),4.95(s,1H,H-1),4.88(dd,J＝10.1,7.9Hz,1H,H-4′),4.21(dd,J＝7.0,5.8 Hz,1H),4.17(d,J＝5.3Hz,1H),4.14–4.08(m,2H),3.73(d,J＝3.9Hz,1H), 3.70–3.63(m,2H),3.57(dd,J＝9.9,7.3Hz,1H),3.42(dt,J＝9.6,6.5Hz,1H), 2.10(s,3H,CH3 CO),1.62–1.56(m,7H,OCH2CH2 CH2 ,CH3),1.54(s,3H,CH3), 1.35(s,3H,CH3),1.33(s,3H,CH3),1.29–1.24(m,19H,CH3-6,(CH2)8),1.15(d, J＝6.3 Hz,3 H,CH3-6′),0.88(t,J＝6.9 Hz,3 H,CH2CH3 )；13C NMR(100 MHz, CDCl3):δ170.23,109.83,109.63,97.02,95.68,78.71,77.08,76.44,76.43,75.77, 74.53,67.88,64.53,63.94,32.06,29.80,29.78,29.77,29.71,29.55,29.49,28.08, 27.81,26.58,26.54,26.30,22.83,21.19,18.06,16.88,14.26。

Claims (5)

1.一种乙酰丙酮银的制备方法，其特征在于包括如下步骤：向硝酸银溶液中加入催化量的双氧水，室温下搅拌10-15min后，加入乙酰丙酮、三乙胺，升温至40-45℃反应1.5-2小时后，过滤，滤液用氯仿稀释、水洗后，有机层经减压浓缩、真空干燥即得乙酰丙酮银(Agacac)。
2.权利要求1所述的制备方法，其特征在于所述硝酸银溶液的浓度为0.1mol/L，双氧水选自质量分数为30％的双氧水，每毫摩尔硝酸银使用10mL乙酰丙酮、0.1mL三乙胺。
3.权利要求1-2任一项所述的制备方法，其特征在于双氧水的用量为每升硝酸银溶液使用2mL双氧水。
4.乙酰丙酮银(Agacac)在催化糖苷化反应中的应用。
5.乙酰丙酮银(Agacac)在催化硫苷类供体与受体发生糖苷化反应中的应用。
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Publication number Priority date Publication date Assignee Title
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CN110283063B (zh) * 2019-06-11 2020-06-16 中山华明泰科技股份有限公司 一种乙酰丙铜镧的制备方法及应用

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