脂肪二胺桥联受阻酚清除DPPH自由基的活性及动力学研究

采用DPPH法对脂肪二胺桥联受阻酚的抗氧化活性和清除反应动力学进行了研究。结果表明,脂肪二胺桥联受阻酚具有良好清除DPPH·的活性,随脂肪二胺桥联受阻酚浓度的增大和清除反应时间的延长,清除活性先快速降低随后变化较小;随着桥联基的增长,清除活性降低,即抗氧化活性降低,这表明脂肪二胺桥联受阻酚的桥联基越长,酚羟基提供氢质子的能力越差,清除自由基的活性越低。然而,该系列受阻酚在聚烯烃材料中,由于受体系相容性的影响,随着桥联基的增长,抗氧化活性反而增强。脂肪二胺桥联受阻酚清除DPPH·的反应为一级反应,且反应速率常数随着桥联基链的增长而降低。     

脂肪二胺桥联受阻酚的合成及抗氧化活性研究

以脂肪二胺为桥联基,通过与β-(3,5-二叔丁基-4-羟基苯基)丙酰氯酰胺化缩合反应,合成了4种脂肪二胺桥联受阻酚.核磁氢谱和质谱证实了脂肪二胺桥联受阻酚的化学结构,采用DPPH法和测氧法对脂肪二胺桥联受阻酚的抗氧化活性进行了研究.结果表明脂肪二胺桥联受阻酚对含氮自由基DPPH和过氧自由基ROO均具有良好的抗氧化活性.随着受阻酚桥联基的增长,受阻酚清除自由基的活性均下降,但随着受阻酚物质的量分数的增加,清除活性均增大,且桥联基对清除DPPH自由基活性的影响大于清除ROO自由基的活性.     

树状聚酰胺-胺桥联受阻酚类抗氧化剂的合成及清除DPPH·活性研究

以系列1.0、2.0代树状聚酰胺-胺(PAMAM)为桥联基,3-(3,5-二叔丁基-4-羟基苯基)丙酰氯为抗氧化基团,通过酰胺化缩合反应合成了系列树状桥联受阻酚类抗氧化剂。红外光谱和核磁共振氢谱证实了系列树状聚酰胺-胺桥联受阻酚类抗氧化剂的化学结构。采用EPR技术研究系列树状聚酰胺-胺桥联受阻酚类抗氧化剂清除DPPH·的能力,结果表明,系列树状聚酰胺-胺桥联受阻酚类抗氧化剂具有良好清除DPPH·活性,且随着清除时间的延长、桥联基长度和代数的增加,其清除活性增强。     

树状桥联半受阻酚类抗氧剂的合成与抗氧化性能

从端基为胺基树状大分子出发, 合成了一种具有多个半受阻酚抗氧化基团、 结构对称的树状桥联半受阻酚类抗氧剂. 元素分析、 傅里叶变换红外光谱(FTIR)、 氢核磁共振波谱(¹H NMR)、 质谱(MS)和冰点降低法证实合成的树状桥联半受阻酚类抗氧剂的化学结构与理论结构一致, 纯度较高. 采用1,1-二苯基-2-苦基肼(DPPH)法和差热扫描量热(DSC)法研究了树状桥联半受阻酚类抗氧剂的抗氧化性能, 并与相应的树状桥联全受阻酚类抗氧剂进行了对比. 研究结果表明, 树状桥联半受阻酚类抗氧剂清除DPPH自由基的活性不仅与清除体系中抗氧剂的浓度有关, 而且与清除时间有关; 清除时间为30 min时的抗氧化能力是清除时间为400 min时抗氧化能力的近2倍. 树状桥联半受阻酚类抗氧剂的半受阻效应使其在DPPH体系和HDPE树脂中的抗氧化能力均优于其相应的树状桥联全受阻酚类抗氧剂.     

超支化分子桥联受阻酚抗氧化剂的合成与表征

以正十八胺为核的1.0代超支化大分子和β-(3,5-二叔丁基-4-羟基苯基)丙酰氯为原料,通过酰胺化缩合反应,合成了一种具有长链烷基和2个受阻酚基团的新型超支化分子桥联受阻酚类抗氧化剂.通过正交实验确定了超支化分子桥联受阻酚类抗氧化剂的最佳合成体系为:3,5-丙酰氯为酰化剂、K_2CO_3为缚酸剂、苯和水为反应溶剂.通过条件优化实验确定了超支化分子桥联受阻酚类抗氧化剂的最佳合成条件为:3,5-丙酰氯与1.0代超支化大分子的物质的量比为6∶1、反应温度为25 ℃、反应时间为12 h、体系苯与水体积比为6∶1、3,5-丙酰氯与缚酸剂K_2CO_3的物质的量比为1∶1,在此条件下,超支化分子桥联受阻酚类抗氧化剂的收率高达75.5%.FT-IR和1H NMR证实了合成抗氧化剂的化学结构与其理论结构相符.超支化分子桥联受阻酚类抗氧化剂在聚乙烯树脂中的抗氧化性能优于抗氧化剂1076,且随着烷基链长度的增加,抗氧化性能增强.     

树状PAMAM桥联受阻酚的合成与表征

以β-(3,5-二叔丁基-4-羟基苯基)丙酰氯(简称3,5-丙酰氯)为原料,以1.0G聚酰胺-胺(PAMAM)为桥联基,通过酰胺化反应合成2种含有4个受阻酚单元的树状PAMAM桥联受阻酚.通过条件优化实验确定最佳反应条件:n(3,5-丙酰氯)∶n(PAMAM)=6∶1;K2CO3为促进剂;苯和水为反应混合溶剂,其中苯用量为40mL,水用量为9.7mL;反应时间15h;反应温度为25℃,此条件下可以得到纯度较高的2种树状PAMAM桥联受阻酚.红外光谱、核磁共振及质谱分析表明,合成的分子与目标分子结构完全相符.     

二甲基硅桥联双芴基钇氯化物的合成与结构

不久前［１］我们报导了二甲基硅桥联双茚基稀土氯化物的合成及表征。从化合物的元素分析、红外光谱、质谱、核磁共振谱等数据,推测该类化合物分子可能的结构为硅桥联的两个茚基分别以η５的形式与中心金属离子成键。最近,我们以芴基代替茚基,合成了二甲基硅桥联双芴基钇氯化物,并用Ｘ－射线衍射法测定了该化合物分子结构。数据表明,该化合物分子中两个芴基是以η５形式与金属钇离子成键。这也说明了我们在前文中所推测出的分子结构的正确性。１　实验部分１．１　主要试剂与仪器氧化钇纯度为９９．９９％（上海跃龙化工厂出产）。其余…     

二(2-羟基苄基)胺的合成及其钠盐结构

二(水杨醛亚胺)甲基-2-苯酚和硼氢化钾进行加氢还原反应,不能得到预期的桥联三酚,会发生C-N键断裂生成了二(2-羟基苄基)胺。二(2-羟基苄基)胺在氢氧化钠溶液中生成季铵桥联的二酚钠盐,其分子结构经过了X光单晶衍射分析表征。     

超支化PAMAM桥联乙烯齐聚用镍系催化剂的合成与表征

以系列直链脂肪胺为核的低代超支化聚酰胺-胺(PAMAM)和水杨醛为原料,通过席夫碱反应制备系列新型超支化PAMAM桥联水杨醛亚胺配体;以无水Ni Cl2为络合试剂,通过络合反应合成系列超支化PAMAM桥联镍催化剂,采用FT-IR和1H NMR证实合成的系列新型配体和镍系催化剂的结构与其理论结构相符.对系列超支化PAMAM桥联镍催化剂催化乙烯齐聚的性能进行了研究,结果表明,超支化PAMAM桥联镍系催化剂配体骨架烷基链长度对其催化活性和选择性影响较小,助催化剂和溶剂影响较大;倍半乙基氯化铝为助催化剂,甲苯为溶剂时,聚合活性较高,产物中C8以上的高碳产物的含量最高;其中以十四胺为核的超支化PAMAM桥联镍催化剂为主催化剂、倍半乙基氯化铝为助催化剂、甲苯为溶剂时,催化乙烯齐聚活性高达1.96×106 g/(mol·h),齐聚产物中C8以上的高碳产物含量为98.77%.     

一种半受阻酚类抗氧剂中间体的合成及抗氧化性能研究

采用2-甲基-6-叔丁基苯酚和丙烯酸甲酯为原料,通过迈克尔加成反应合成半受阻酚类抗氧剂中间体β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸甲酯.条件优化实验确定该抗氧剂中间体的最佳合成工艺条件为:2-甲基-6-叔丁基苯酚与丙烯酸甲酯物质的量之比为1∶1.1,催化剂KOH与2-甲基-6-叔丁基苯酚的物质的量比为1∶10,丙烯酸甲酯滴加温度为90℃,丙烯酸甲酯滴加时间为30 min,反应温度为130℃,反应时间为5 h.在此条件下,半受阻酚类抗氧剂中间体β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸甲酯的收率大于70%,熔程41.6℃~44.0℃.IR和1H NMR证实所合成目标产物的化学结构与其理论结构相一致.DPPH法测定半受阻酚类抗氧剂中间体清除自由基的性能,并与全受阻酚类抗氧剂中间体β-(3,5-二叔丁基-4-羟基苯基)丙酸甲酯进行对比.结果表明,由于邻位取代基的不对称效应,使得空间位阻较小的不对称抗氧剂中间体β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸甲酯清除DPPH·的活性高于邻位取代基空间位阻较大的对称抗氧剂中间体清除DPPH·的活性.     

Kinetics and structure-activity relationship of dendritic bridged hindered phenol antioxidants to protect styrene against free radical induced peroxidation

A series of dendritic poly(amido-amine) (PAMAM) bridged hindered phenols antioxidants were synthesized. The active antioxidant group (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid) was attached to two generations of PAMAM dendrimers, and their structure was verified by nuclear magnetic resonance (NMR) and fourier transform infrared spectra (FT-IR). The antioxidant abilities of the dendritic phenols to inhibit the oxidation of styrene were evaluated and the relationships between the length of core, the generation of dendrimers and the antioxidant activities were established. The reaction kinetics of scavenging peroxyl radicals was followed by oxygen consumption. The inhibition time (t_inh) values showed the dendritic phenols had the ability of scavenging peroxyl radicals, and that the antioxidant ability increased with the increasing length of the core and the generation. The kinetic analysis demonstrated that dendritic phenols could slow the rate of styrene peroxidation induced by AIBN, as shown by the number of trapping ROO· (n), and this role was in accordance with that of the t_inh values.     

Synthesis,antioxidant properties,and reaction kinetics of aliphatic diamine bridged hindered phenols

Russian Journal of General Chemistry - A series of aliphatic diamine bridged hindered phenols was synthesized. Their antioxidant activity was evaluated for assessing the role of bridging groups in...     

苯并呋喃酮衍生物结构对其DPPH捕获能力的影响

采用自由基比色法考察苯并呋喃酮衍生物结构对其DPPH捕获能力的影响。结果发现,母体苯环5,7位上甲基和叔丁基的改变以及取代苯环上强供电子取代基的存在对苯并呋喃酮衍生物的DPPH捕获能力没有明显影响。取代苯环2’位存在明显的位阻作用,对苯并呋喃酮衍生物的DPPH捕获能力具有明显的抑制作用：并且当此位为不含活泼氢的氢键受体取代基时,苯并呋喃酮衍生物的DPPH捕获能力会由于取代基与3位活泼氢的氢键作用而被进一步削弱;但此位为含有活泼氢的氢键受体取代基时,此取代基的氢将会由于3位活泼氢与取代基的氢键作用而活化,从而使其位阻作用得到一定程度的抑制。     

Thiacalix[4]arene derivatives with proximally bridged lower rim

New types of lower rim proximally bridged thiacalix[4]arenes have been prepared by direct aminolysis of starting tetraacetate derivative in the cone conformation using aliphatic α,ω-diamines. X-ray crystallography revealed the highly preorganized array of -C(O)NH- bonds resulting in strong intramolecular hydrogen bonding between amide groups of both bridges. The length of the corresponding diamine was found to have an essential influence on the yield of these bridged molecules.     

Chemoselective and efficient carbomethoxylation of the alcoholic chain of phenols by dimethyl carbonate (DMC)

The efficiency of dimethyl carbonate (DMC) as chemoselective carbomethoxylating agent of the alcoholic chain of phenols has been investigated. In the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or sulfuric acid as catalysts, new carbomethoxylated phenolic compounds were obtained in quantitative yields. A new efficient derivatization of the aliphatic alcoholic chain of the precious natural hydroxytyrosol is described, which increases the lipophilicity of the hydroxytyrosol. The antioxidant activity of this new carboxymethylated hydroxytyrosol 8 has been investigated using DPPH radical scavenging test. The results showed that this new compound has an antioxidant activity similar to hydroxytyrosol.     

Synthesis of aliphatic–aromatic polyamides by palladium-catalyzed polycondensation of aliphatic diamines,aromatic dibromides,and carbon monoxide

Aliphatic–aromatic polyamides were synthesized by the palladium-catalyzed polycondensation of aliphatic diamines, aromatic dibromides, and carbon monoxide. The effects of variables, such as the kind and amount of base, reaction temperature, and the kind of palladium catalyst were investigated in detail on the reaction of hexamethylenediamine and bis(4-bromophenyl) ether with carbon monoxide. Inherent viscosities of the polyamides were between 0.13 and 1.21 dL/g and varied markedly with the structure of the diamine component. Solubility of the polyamides decreased with increase of chain length of aliphatic diamines, and the polyamides derived from p-dibromobenzene was insoluble in organic solvents except for m-cresol. Polyamides obtained from primary aliphatic diamines began to decompose at 210–250°C in air due to decomposition of the aliphatic chain.     

红花黄色素抗氧化活性研究

通过考察红花黄色素(SY)及其主要化学成分对羟基自由基介导2-脱氧核糖氧化降解的抑制作用,以及对1,1-二苯基-2-苦肼基自由基(DPPH·)的清除能力,探究SY的体外抗氧化活性及其抗氧化的主要有效成分.通过Fenton反应产生羟基自由基,用紫外分光光度计检测了SY及其主要化学成分对2-脱氧核糖降解的抑制作用和对DPPH·的清除能力,同时对红花黄色素B(SYB)抑制2-脱氧核糖降解的作用机制做了初步研究.结果表明SY抑制Fenton反应对2-脱氧核糖的氧化降解的IC50为256.79 μg/mL,对DPPH·清除的IC50值为27.15μg/mL.羟基红花黄色素A(HSYA)和SYB是SY中抗氧化的两个有效成分,抑制2-脱氧核糖的氧化降解的IC50分别为220.68 μg/mL和207.01μg/mL;对DPPH·清除的IC50值分别为55.81 μg/mL和41.25μg/mL.SYB对2-脱氧核糖氧化降解的抑制作用机理研究表明,SYB除了对Fenton反应产生的羟基自由基具有直接清除作用外,又可通过与Fe2+离子的络合作用而阻断Fenton反应产生羟基自由基.由此可知SY具有明显的体外抗氧化活性,SYB和HSYA为其主要抗氧化活性成分.     

Syntheses and Characterization of Ten-Membered Cyclic and Large Bite Acyclic Bis(phosphines)

Reaction of bis(dichlorophosphino)aniline with CH 2 bridged bis(phenols) or substituted diamine gives the 10-membered heterocyclic phosphorochloridities in quantitative yield. The bis(phenols) also react with chlorodiphenylphosphine to afford the bulky acyclic bis(phosphinites).     

Influence of the bridging ligand on the substitution behaviour of dinuclear Pt(II) complexes. An experimental and theoretical approach

A series of dinuclear Pt(II) complexes of the type [Pt2(N,N,N',N'-tetrakis(2-pyridylmethyl)diamine(H2O)2]4+ were synthesized. Acid-base titrations, and concentration and temperature dependent stopped-flow measurements of the reaction with chloride were performed to study the thermodynamic and kinetic behaviour of the dinuclear bridged complexes. The results indicate that there is a clear interaction between the two Pt(II) centres, which becomes weaker as the aliphatic chain increases in length. From a certain chain length onwards, the Pt(II) centres become independent of each other and exhibit identical thermodynamic and kinetic properties. The experimental results are discussed in reference to structures obtained by DFT (BP86/LACVP*) calculations.