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P-Phos [2,2′6,6′-四甲氧基吡啶-4,4′-二(二苯基膦)-3,3′-联吡啶]是一类对空气稳定的杂环磷配体。本文以较简单的方法合成了rac-P-Phos配体,并用IR、1H NMR、13C NMR和元素分析等方法进行了表征。首次将P-Phos配体用于催化卤代芳烃和胺的偶联反应中。通过对碱、溶剂和催化剂用量等的筛选,确立了最优化的反应条件。配体对溴代芳烃的催化效果很好,对具有吸电子存在的氯代芳烃,特别是氯代吡啶同样得到了令人满意的结果,分离产率高达97%。催化剂对水和空气的稳定性很好,对胺偶联反应的催化效果很理想,因此是一种有应用前景的催化剂。 相似文献
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以氯代芳烃为底物,季鏻盐[PPh4]Br为助催化剂,用于环钯催化的Heek芳基化反应.结果表明,在环钯-[PPh4]Br催化体系中,以Na2CO3作为碱性试剂,使用0.3mol%Pd的环钯催化剂催化氯苯的Heek反应,就可得到比较高的产率(88%)和转化率(90%).对于大部分卤代芳烃Heck反应而言,环钯-[PPh4]Br是一种有效的催化体系,即使是对含推电子基团的不活泼的氯代芳烃,在此体系中也能获得比较好的结果.此外,文中还探讨了反应温度、[PPh4]Br/Pd比值及催化剂回用对反应活性的影响. 相似文献
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铜催化卤代芳烃进行氨解反应是构建碳氮键的重要方法。铜作为催化剂不仅便宜、丰富、相对低毒,而且可以通过几个氧化态进行循环催化。配体的发展则扩展了底物的适用范围,提高了官能团的兼容性和反应的选择性,使得该反应成为一种通用的制备芳胺的方法。本文以铜盐催化剂为线索,对该反应机理进行了简介,对近年来铜催化卤代芳烃的氨解反应的研究进展进行了综述和展望,并指出高活性和高选择性的催化体系依然有限,铜催化剂使用量仍然较大,氨和氯代芳烃的使用还不够广泛,而且关于该类反应详细机理的文献报道还缺乏。此外,发展一个新的、高效的和通用的氨解方法仍然显得极为迫切。 相似文献
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我们发展一种在催化体系可回收和无配体条件下溴化四丁基铵(TBAB)中钯催化卤代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应方法。我们发现水的量对反应有很大的影响。当水的用量为1 %(质量比)时,反应的结果最好。在3 mol%的醋酸钯和1.5 g的TBAB(含1%的水),一系列卤代芳烃与芳基硼酸的顺利地发生Suzuki-Miyaura交叉偶联反应,得到中等及良好的产率。而且在溴代芳烃和活泼的氯代芳烃的交叉反应中,Pd(OAc)2/TBAB催化体系可以回收重复使用多次,并且催化活性基本不变。 相似文献
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氯化钕配合物在4—乙烯吡啶聚合反应中的催化作用 总被引:3,自引:0,他引:3
氯化钕配合物是双烯烃聚合催化剂组分之一 ,与烷基铝所构成的二元体系对丁二烯聚合具有较佳活性 [1,2 ] ,但用氯化钕配合物催化极性单体的聚合反应尚未见报导 .极性单体的聚合是人们感兴趣的课题 ,例如 Benito等 [3 ]用过渡金属化合物 (VCl3-Al Et3)体系催化聚合 4-乙烯吡啶 (4VPy)极性单体 .但是它的催化活性较低 ,催化效率为 3.1×1 0 -4 kg· mol-1· h-1.我们研究了将含少量的氯化钕配合物催化剂用于该聚合反应 ,催化活性得到很大提高 ,催化效率达到 50 .71 Kg· mol-1· h-1.表明氯化钕配合物催化体系不仅对双烯烃而且对极性单体聚… 相似文献
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A polystyrene-bonded stannic chloride catalyst was synthesized by the method of lithium polystyryl combined with stannic chloride. This catalyst is a polymeric organometallic compound containing 0.25 mmol Sn (Ⅳ)/g catalyst. The catalyst showed sufficient stability and catalytic activity in organic reaction such as esterification, acetalation and ketal formation, and it could be reused many times without losing its catalytic activity. 相似文献
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A nonmetal catalytic system consisting of N-hydroxyphthalimide, xanthone, and tetramethylammonium chloride was developed. A wide range of hydrocarbons could be oxidized efficiently with dioxygen under mild conditions. In the presence of xanthone and tetramethylammonium chloride, catalytic activity of N-hydroxyphthalimide was greatly improved, and selectivity for alkyl hydroperoxide was remarkably decreased. 相似文献
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Bulk polymerization of ε-caprolactone(CL) with neodymium chloride-epoxide sys tem has been studied. It was found that the addition of epoxide can greatly increase the catalytic activity of neodymium chloride. The catalytic activity sequence of NdCl3 combined with epoxide is: NdCl3-ethylene oxide > NdCl3-proplene oxide > NdCl3-epichlorohydrin≈NdCl3-allyl glycidyl ether. The catalytic activity of NdCl3-proplene oxide system increases,but molecular weight of resulting polycaprolactone(PCL) decreases at higher proplene oxide/ neodymium chloride molar ratio.The molecular weight of PCL can be controlled by catalyst concentration. Higher polymerization temperature can greatly increase the catalytic efficien cy. At 30℃, PCLwith molecular weight as high as 28. 9×104can be prepared easily with an activity of 44×104g PCLper molar neodymium, and at 60℃, the molecular weight of PCLand catalytic efficiency increased to 42×104and 106g PCL/mole Nd respectively. 相似文献
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Yu. N. Bespal’ko E. N. Shved N. M. Oleinik 《Theoretical and Experimental Chemistry》2008,44(5):300-306
A study was carried out on the kinetics of the reaction of 1-chloro-2,3-epoxypropane (epichlorohydrin, ECH) with aliphatic
carboxylic acids in the presence of (3-chloro-2-hydroxypropyl)trimethylammonium (CHPTMA) chloride obtained by trimethylammonium
chloride and ECH. We compared the catalytic activity of CHPTMA chloride, trialkylamines, and tetraalkylammonium halides and
evaluated the effect of their structure. An ab initio quantum-chemical calculation was performed to obtain a detailed analysis
of the state of the catalysts in this system in order to understand the peculiarities of catalytic activity of these bases.
Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 44, No. 5, pp. 292–297, September–October, 2008. 相似文献
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采用浸渍法制备了羟基磷灰石(HAP)负载的路易斯酸SnCl2和SnCl4催化剂.它们在三糖在醇溶液中转化为乳酸酯反应中表现出一定的催化活性.在最佳的反应条件下,SnCl2/HAP催化1,3-二羟丙酮在正丁醇溶液中转化为乳酸正丁酯,收率高达73.5%. 相似文献
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