离子型有机锡化合物分子结构研究

文章结合笔者近年来的工作总结了离子型有机锡化合物在分子结构上的特征,研究结果可以对离子型有机锡化合物的合成和生物活性研究起到指导性作用。     

海产品或海水中有机锡检测方法研究进展

有机锡(Ⅳ)化合物具有良好的反应活性和生物活性,被广泛应用于催化、合成、医药、PVC稳定剂、防污、防腐、杀菌等各个方面,但是此类化合物大多具有生物毒性,由其引发的环境污染正日益受到各国科学家们的关注.在简要介绍有机锡的生物毒性、近年来我国沿海地区有机锡污染现状的基础上,重点从有机锡的检测原理出发,综述了2000年以来国内外学者在有机锡分析测试方法上的研究进展情况,并对未来的发展趋势作了展望.     

有机锡聚酯的合成及其性质的研究

利用界面缩聚技术,将R_2S_nCl_2与二酸在高度搅拌下反应,制成了一系列新的有机锡聚酯化合物。 对搅拌速度、反应温度、反应介质、反应时间与产率及分子量的关系进行了讨论。对部分高聚物对PVC热稳定性的影响进行了测试,取得了有意义的结果。     

三烃基锡化合物的合成及应用

本文介绍了三烃基有机锡化合物的生化性质及合成方法。并对三烃基有机锡化合物在农作物保护、杀菌防腐等方面的应用情况进行了讨论。     

含硅有机锡化合物催化合成水杨酸苄酯的研究

以合成水杨酸苄酯为例,考察了含硅有机锡化合物在酯化反应中的催化活性,探讨了催化剂用量、反应时间和溶剂等因素对反应的影响。实验结果表明,4种含硅有机锡化合物在水杨酸和苄醇的反应中均表现出一定的催化活性,其中二[（三甲基硅基）亚甲基]二氯化锡的催化活性较高,在催化剂用量为3．0％（反应物料的质量分数）,甲苯为溶剂,酸醇比1...     

含硅有机锡化合物在酯化反应中的催化性能研究

考察了含硅有机锡化合物在酯化反应中的催化活性,并以合成乙酸异戊酯的反应为例,探讨了影响反应的各种因素。其中,三[(三甲基硅基)亚甲基]氯化锡的催化活性最高,在催化剂用量1.5%,反应时间5h条件下,酯化率达到93.7%。     

一维链状有机锡化合物(PhCH2)3SnCl的合成、表征及晶体结构

利用苄基氯和锡反应，合成了一维链状有机锡化合物(PhCH2)3SnCl。通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征。用X-射线单晶衍射测定了该化合物的晶体和分子结构。锡原子呈畸变四面体构型。通过化合物分子间Sn…Cl作用，形成一维链状结构。     

有机锡化合物催化剂在有机反应中的应用

有机锡化合物具有独特的催化活性,在聚合、加成、酯化和还原等有机合成反应中广泛应用.本文综述了近十年来有机锡化合物在催化领域里的研究进展.     

微波辐射下有机锡催化合成对羟基苯甲酸甲酯

本文以磺基水杨酸和二丁基氧化锡为原料合成了二丁基锡(IV)磺基水杨酸酯,并以此为催化剂,在微波辐射下合成了对羟基苯甲酸甲酯.文中探讨了微波功率、催化剂用量、反应时间、温度及醇酸摩尔比对酯合成收率的影响.实验结果表明,有机锡化合物在微波辐射下对酯化反应有良好的催化活性,对羟基苯甲酸甲酯的收率可达到93％.     

酯交换法合成甲基丙烯酸二甲胺基乙酯

以甲基丙烯酸甲酯、二甲氨基乙醇为原料，有机锡化合物为催化剂，吩噻嗪为阻聚剂，采用酯交换法合成了甲基丙烯酸二甲胺基乙酯。确定了合成的最佳工艺，即甲基丙烯酸甲酯与二甲氨基乙醇的量比为2．2：1．0，催化剂用量为反应液总质量的1．2％，阻聚剂用量为反应液总质量的0．2％，反应温度为体系回流温度，在此条件下，产率达96％以上。     

新型抗乳腺癌药帕博西尼的合成进展

帕博西尼（palbociclib）是一种治疗转移性乳腺癌的新药,于2015年获得美国食品药品监督管理局批准上市。本文较全面地报道了帕博西尼的9种合成工艺路线,并进行了相应的评价。通过对这些合成工艺的比较和分析,发现帕博西尼的合成主要包括4个关键步骤：构建吡啶酮并嘧啶环、2位引入[5-（1-哌嗪基）-2-吡啶基]氨基、6位引入乙酰基和8位引入环己基。传统的合成路线存在诸多缺点,如反应步骤多、采用价格昂贵的金属钯以及有毒的有机锡化物和强碱二（三甲基硅基）胺基锂（LiHMDS）、部分操作条件苛刻和总收率低。新开发的路线或通过选择恰当的原料和反应,或选用新型反应器如微波-超声波联合反应器,或通过“一锅煮”方式来减少反应步骤,避免采用钯类和有机锡类化合物,从而构建反应步骤少、收率高、环境友好和较具有工业化价值的合成路线。帕博西尼的合成路线总体上向着原辅材料价廉易得、所采用试剂环保、反应路线短、操作简单、反应条件温和及总收率高的方向不断改进。就现有的合成路线而言,倘若能寻找到操作简单的催化剂代替强碱LiHMDS,以2,4-二氯嘧啶为起始原料的合成路线8具有较强的工业化前景;倘若能解决微波-超声波联合反应器的放大问题,以2-乙酰基-2-丁烯酸甲酯为起始原料的合成路线6是最具工业化前景的路线。此外,本文也介绍了具有更好的药代性质和体内稳定性的氘代帕博西尼的合成工艺,可根据帕博西尼的先进合成路线对此工艺进行改进。     

有机锡催化碳酸乙烯酯与丁二酸二甲酯耦合反应

以含有不同取代基的有机锡化合物为催化剂,通过碳酸乙烯酯（EC）与丁二酸二甲酯（DMSu）耦合法制备了聚丁二酸乙二醇酯（PES）和碳酸二甲酯（DMC）,并对PES的结构进行了表征。结果表明,有机锡取代基团的电子效应和空间位阻对其催化性能具有很大影响;取代基的吸电子效应越大、空间位阻越小,有机锡的催化活性越高,但若有机锡中存在B酸中心时则容易引起副反应,导致产物选择性差。综合考虑,Bu₂SnO的催化性能最好,最优反应条件下,DMC的收率可达到70.08%,PES的特性黏数可达到0.622 dl·g^-1。     

In Situ Preparation of Functional Heterogeneous Organotin Catalyst Tethered on SBA-15

A stable heterogeneous organotin catalyst has been prepared by in situ tethering organotin compounds on SBA-15. This was verified by XRD, TEM, N₂ adsorption/desorption at −196 °C, FTIR and diffuse reflectance UV–vis spectral techniques. This material was much more active than the sample prepared by the grafting method for the direct synthesis of dimethyl carbonate (DMC) from methanol and CO₂ despite that its catalytic activity was dependent on the organotin amount. This could be attributed to the formation of organotin clusters with different structures and the larger surface area. After immobilization on the SBA-15 mesoporous material, the six-coordinated organotin clusters showed higher activity, compared to the tetrahedral Sn species. With increasing reaction temperature and CO₂ pressure, the catalytic activity considerably increased.     

Catalysis of the isocyanate-hydroxyl reaction by non-tin catalysts

Tin compounds, especially dibutyltin dilaurate, are in widespread use in coatings as catalysts for the isocyanate/hydroxyl reaction. Because of the high aquatic toxicity of some organotin compounds, there has been an attempt to ban organotin compounds from all coating applications. As a general rule organotin catalysts are not selective, they catalyze the reaction of isocyanates with both hydroxyl groups and water and also catalyze the hydrolysis of ester groups. We are interested in finding alternatives to these catalysts and in developing compounds which exhibit increased selectivity for the isocyanate/hydroxyl reaction. In addition, we are interested in developing materials which give a longer potlife and enhanced reaction rates. We will report on various metal salts and chelates we have investigated, the mechanism of catalysis and application characteristics in both high solids and water-borne applications. We found zirconium chelates activates the hydroxyl groups and catalyze the isocyanate-hydroxyl reaction by an insertion mechanism. This reaction is selective and preferred over the isocyanate-water reaction. This permits the use of this catalyst in waterborne isocyanate crosslinked two component coatings. In addition this catalyst permits very high reaction rate which suggests is use in plural component gun applications.     

N-亚甲基磷酸壳聚糖有机锡酯的合成、表征及杀螺活性研究

用磷酸和甲醛在稀醋酸介质中对壳聚糖(CTS)进行N-亚甲基磷酸化改性,得到N-亚甲基磷酸壳聚糖(MPCS),用自制的MPCS在苯或甲苯介质中与有机锡发生反应,合成了3个新的N-亚甲基磷酸壳聚糖有机锡酯化合物:MPCS-SnPh3、MPCS-Sn(PhCH2)3、MPCS-SnBu3。通过IR、13C NMR、TG/DTA和X-ray对其结构和性质进行了表征和测试。杀钉螺实验结果表明,当其浓度在1.00 mg/L以上时,浸杀48 h后,钉螺的死亡率达100%。     

钯配合物在形成碳-碳键偶联反应中的催化作用

报道了纤维素氧膦 -钯配合物在有机锡试剂与酰氯化合物形成碳 -碳键的交叉偶联反应中的催化作用 ,并对部分反应条件及反应机理进行了研究和探讨。     

Interference between reactants in simultaneous interpenetrating polymer network formation. II. Influence of the presence of a free‐radical initiator on polyurethane formation

Polyether polyurethane networks were prepared in solution at 25 and 60°C, using various organotin catalysts. The presence of a free‐radical initiator [viz. azobisisobutyronitrile (AIBN)] in the reaction media has no effect on the catalytic efficiency of organotin(IV) compounds, whereas it causes severe deactivation of organotin(II) compounds. This effect was explained by the following mechanism: formation of a cyclic 1 : 1 complex by coordination of the nitrile groups of AIBN with the tin(II) atom, which both reduces the effective catalyst concentration and allows the early decomposition into radicals, as previously seen, leading to tin oxidation. The addition of a free‐radical scavenger such as 3‐tert‐butyl pyrocatechol allows the maintenance of the catalyst efficiency of organotin(II) compounds at their reference level. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1929–1937, 2002     

Synthesis of Polystyrene-Bound Organotin Derivatives as Intermediates for the Production of Hybrid Materials

Polystyrenes bearing tricyclohexylstannyl moieties with different stereoregularities, molecular weights, and chemical composition have been prepared and characterized through two synthetic routes. The suitability of the products obtained to be used as intermediate derivatives in the synthesis of the corresponding organotin trichlorides, precursors to organic–inorganic hybrid materials, has been investigated.