CN108976112B - 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

Info

Publication number
CN108976112B
CN108976112B CN201810781981.6A CN201810781981A CN108976112B CN 108976112 B CN108976112 B CN 108976112B CN 201810781981 A CN201810781981 A CN 201810781981A CN 108976112 B CN108976112 B CN 108976112B
Authority
CN
China
Prior art keywords
silver
preparation
acetylacetonate
silver acetylacetonate
hydrogen peroxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810781981.6A
Other languages
English (en)
Other versions
CN108976112A (zh
Inventor
于晓萍
王斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yangzhou Polytechnic Institute
Original Assignee
Yangzhou Polytechnic Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yangzhou Polytechnic Institute filed Critical Yangzhou Polytechnic Institute
Priority to CN201810781981.6A priority Critical patent/CN108976112B/zh
Publication of CN108976112A publication Critical patent/CN108976112A/zh
Application granted granted Critical
Publication of CN108976112B publication Critical patent/CN108976112B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • 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
    • 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
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • 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
    • 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
    • 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

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
Figure BDA0001731268180000011
(Tol为4-甲基-苯基)，受体优选
Figure BDA0001731268180000012
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
Figure BDA0001731268180000021
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 (3)

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。
CN201810781981.6A 2018-07-16 2018-07-16 一种乙酰丙酮银的制备方法及其作为催化剂的用途 Active CN108976112B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810781981.6A CN108976112B (zh) 2018-07-16 2018-07-16 一种乙酰丙酮银的制备方法及其作为催化剂的用途

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810781981.6A CN108976112B (zh) 2018-07-16 2018-07-16 一种乙酰丙酮银的制备方法及其作为催化剂的用途

Publications (2)

Publication Number Publication Date
CN108976112A CN108976112A (zh) 2018-12-11
CN108976112B true CN108976112B (zh) 2021-12-14

Family

ID=64549788

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810781981.6A Active CN108976112B (zh) 2018-07-16 2018-07-16 一种乙酰丙酮银的制备方法及其作为催化剂的用途

Country Status (1)

Country Link
CN (1) CN108976112B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6613924B1 (en) * 1999-11-23 2003-09-02 Research Foundation Of State Of New York Silver precursors for CVD processes
CN1737006A (zh) * 2005-07-18 2006-02-22 昆明贵金属研究所 二(乙酰丙酮)合钯(ⅱ)的合成方法
CN101157605A (zh) * 2007-10-19 2008-04-09 扬州市兴业助剂有限公司 一种乙酰丙酮铜的生产方法
CN105085585A (zh) * 2014-05-11 2015-11-25 于跃 一种鼠李糖苷类化合物及其作为抗多药耐药肿瘤药物的应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI527821B (zh) * 2013-10-16 2016-04-01 國立中山大學 銀化合物、銀墨水及可撓式基板之噴印方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6613924B1 (en) * 1999-11-23 2003-09-02 Research Foundation Of State Of New York Silver precursors for CVD processes
CN1737006A (zh) * 2005-07-18 2006-02-22 昆明贵金属研究所 二(乙酰丙酮)合钯(ⅱ)的合成方法
CN101157605A (zh) * 2007-10-19 2008-04-09 扬州市兴业助剂有限公司 一种乙酰丙酮铜的生产方法
CN105085585A (zh) * 2014-05-11 2015-11-25 于跃 一种鼠李糖苷类化合物及其作为抗多药耐药肿瘤药物的应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Solution-based b-diketonate silver ink for direct printing of highly conductive features on a flexible substrate;Chen-Ni Chen等;《Journal of Materials Chemistry C》;20130626;第1卷;5161-5168 *

Also Published As

Publication number Publication date
CN108976112A (zh) 2018-12-11

Similar Documents

Publication Publication Date Title
Keck et al. New allylstannanes for the connective construction of monoprotected vicinal diols
Ma et al. Synthesis and characterization of copper (II) 4′-phenyl-terpyridine compounds and catalytic application for aerobic oxidation of benzylic alcohols
Kayastha et al. Versatile gold catalyzed transglycosidation at ambient temperature
CN107129499B (zh) 含咪唑环的稠杂环类化合物及其制备方法和应用
Han et al. Incorporation of metal ions into silica-grafted imidazolium-based ionic liquids to efficiently catalyze cycloaddition reactions of CO 2 and epoxides
CN108976112B (zh) 一种乙酰丙酮银的制备方法及其作为催化剂的用途
CN108067301A (zh) 一种季铵盐离子液体聚合物催化剂在co2环加成反应中应用
CN105254693B (zh) 一种泰地罗新的合成方法
CN104910104B (zh) 一种利用铜催化合成二氢呋喃衍生物的方法
CN109369356A (zh) 一种环己烯选择性氧化制备1,6-己二醛方法
Wu et al. Green synthesis of palladium nanoparticles via branched polymers: a bio-based nanocomposite for C–C coupling reactions
Nemoto et al. Synthesis of a water-soluble o-carbaborane bearing a uracil moiety via a palladium-catalysed reaction under essentially neutral conditions
CN105601942B (zh) 一种基于InIII的金属有机骨架及其制备方法和应用
CN111995516A (zh) 一种二氟乙酰氟的合成方法
CN108947754B (zh) 双齿亚磷酸酯配体在c-f键构建反应中的应用
CN105503608B (zh) 生产碳酸乙烯酯的方法
CN105037081B (zh) 一种联苯基烯烃化合物的三氟甲基化方法
CN106977555A (zh) 一种固体酸催化糖类全乙酰化的方法
CN107686457A (zh) 一种亚铁盐催化的两组分反应合成3‑苯硫基‑2，4‑苯戊二烯酸乙酯化合物的方法
CN110078709B (zh) 一种二价锌离子的金属有机配合物及其制备方法与应用
CN110054603A (zh) 一种芳基碳苷类化合物的合成方法
CN109369517A (zh) 一种治疗乳腺癌药物用中间体的制备方法
RU2263656C1 (ru) Способ получения 1,3-дихлорпропанола-2
CN112409236B (zh) 一种高选择性合成3-硫醚吲哚的方法
CN101514182B (zh) β,β’-二(4-吡啶基)二乙烯基苯的制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant