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以2-萘酚和80%水合肼为起始原料,经3步反应生成光学活性的2,2’-二胺-1,1’-联萘,该对映体再依次经过溴代、锂化及羧基化反应制备得到了手性1,1’-联萘-2,2’-二甲酸,收率为68.4%(以2,2’-二溴-1,1’-联萘计),光学纯度为84%。各步产物的结构经1H NMR、13C NMR得到确证。该反应原料价廉易得,整个操作过程简单安全,具有一定的应用研究价值。 相似文献
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手性是与生活休戚相关的一种自然属性,利用手性催化剂催化反应的进行是最有效的一种不对称催化合成反应方法。离子液体所具有的可设计性结构,以及黏度低、不易挥发、无异味、绿色环保等优良性质使其近年来受到化学工作者们的广泛青睐。将手性配体与功能化离子液体耦合,合成一种全新的具有不对称诱导和控制功能的手性离子液体催化剂,并用于反应考察其催化活性,得到了苯乙烯氢甲酰化的最优反应工艺条件为甲苯作溶剂,对叔丁基邻苯二酚作阻聚剂,反应温度60℃,合成气p(CO/H_2)=2 MPa,n(CO)∶n(H_2)=1,持续反应4 h。在该反应条件下,苯乙烯的转化率为84.9%,2-苯基丙醛收率为76%,e.e.值为84%。 相似文献
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以均苯三酚为原料,经两步反应制得芒果苷元合成中的重要中间体2-溴-4,5,2’,4’,6’-五甲氧基二苯甲酮。第一步,均苯三酚在Me2CO3/K2CO3/DMSO(二甲基亚砜)反应体系中于120~150℃下完成全甲基化得到均苯三酚三甲醚,收率约95%;第二步,以1,2-二氯乙烷为溶剂,均苯三酚三甲醚与2-溴-4,5-二甲氧基苯甲酸在POCl3的作用下于70~80℃下发生Friedel-Crafts酰基化反应,得到目标化合物,收率约85%。目标化合物为全新化合物,其结构经IR、UV、EIMS、13 CNMR1、HNMR所确证。 相似文献
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近年来,手性磷酸被广泛应用于催化不对称反应。通过以手性(R)-BINOL为原料,在联萘骨架的3,3’-位上通过醚化、取代、磷酸化等制备得到喹啉取代的新型含联萘骨架的手性Brnsted酸催化剂。所有化合物的结构用核磁碳谱、氢谱对进行了标征鉴定。我们并对目标化合物的刚性结构进行了讨论。 相似文献
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3,3’-位杂原子取代的BINOL类手性催化剂在不对称合成中的应用 总被引:1,自引:0,他引:1
从一系列3,3’-位杂原子取代的BINOL(1,1’-联二萘酚)类手性催化剂不对称催化反应类型的不同,探讨了3,3’-位杂原子取代的BINOL类手性催化剂在不对称合成中应用的研究进展,指出3,3’-位杂原子取代的BINOL类手性催化剂不对称催化底物高效的对映体选择性,并对该类手性催化剂的发展进行了展望。 相似文献
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以(S)-(-)-1,1'-联萘-2,2'-二酚为原料,经三氟甲基磺酸基保护后与二苯基氧膦偶联,最后经三氯硅烷还原得到(S)-(-)-2,2'-双二苯基膦基-1,1'-联萘,采用~(31)PNMR、~1HNMR和HRMS对目标化合物进行结构表征,通过考察各步的反应条件,得出最佳的工艺条件:n〔(S)-(-)-1,1'-联-2-萘酚二(三氟甲磺酸酯)〕∶n(二苯基氧膦)∶n(1,4-二氮杂二环[2.2.2]辛烷)∶n〔Ni(dppe)Cl_2〕∶n(HSiCl_3)=1∶2.1∶2.5∶0.1∶3,在催化偶联步骤反应温度为100℃,反应时间为48 h,三氯硅烷还原步骤加热回流5 h,得到手性2,2'-双二苯基膦基-1,1'-联萘的收率可达82.3%,e.e.值为99.3%。 相似文献
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新型二羟基手性磷酸催化剂的合成 总被引:1,自引:0,他引:1
以1,1'-联二萘酚〔(R)-BINOL〕为原料,在n-BuLi的作用下对BINOL的3,3'位上进行修饰,获得(R)-3,3'-双(二苯基羟基甲基)-2,2'-二羟基-1,1'-联二萘(Ⅰc),并通过羟基选择性保护,磷酸化反应,将其转化为具有潜在能力的手性磷酸催化剂(Ⅱa),收率52%。 相似文献
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W. Werner D. Tresselt W. Ihn G. Ziebell 《Advanced Synthesis \u0026amp; Catalysis》1987,329(6):1031-1037
Resolution of the Enantiomers of (S,R)-1,1′-Bi-2,2′-naphthylhydrogenphosphate by (1R,2R)- and (1S,2S)-2-Amino-1-(4-nitrophenyl)-propane-1,3-diol The resolution of the diastereoisomeric salts of the title compounds was possible in the presence of a ketone, especially acetone, which forms oxazolidines ( 3a–d ) with the chiral bases. These oxazolidines afforded separable salts with the (S,R)-1,1′-Bi-2,2′-naphthylhydrogenphosphate ( 4 ). The structures of these salts were proved by m.s. and n.m.r. spectroscopy. 相似文献
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Ian Gosnay Ernst D. Bergmann M. Rabinovitz I. Agranat 《Israel journal of chemistry》1972,10(2):423-437
In order to obtain a better insight into the fine-structure of dibiphenylene-ethene, the 1,1′-difluoro-, 1,1′-dichloro, 1,1′- and 2,2′-dimethyl derivatives have been prepared using a variety of methods. The attempted preparation of the pure 1,1′-dibromo-derivative failed. 相似文献
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Wei Li Guohua Hou Mingxin Chang Xumu Zhang 《Advanced Synthesis \u0026amp; Catalysis》2009,351(18):3123-3127
A catalytic method employing the cationic iridium‐(Sc,Rp)‐DuanPhos [(1R,1′R,2S,2′S)‐2,2′‐di‐tert‐butyl‐2,2′,3,3′‐tetrahydro‐1H,1′H‐1,1′‐biisophosphindole] complex and BARF {tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate} counterion effectively catalyzes the enantioselective hydrogenation of acyclic N‐arylimines with high turnover numbers (up to 10,000 TON) and excellent enantioselectivities (up to 98% ee), achieving the practical synthesis of chiral secondary amines. 相似文献
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通过草酰二肼与1,1′-二羟基-5,5′-联四唑(BTO)溶液的质子化反应制备了1,1′-二羟基-5,5′联四唑的一草酰二肼盐(BTOOH),产率达到92%;培养了BTOOH的单晶,用X射线单晶衍射和TG-DSC分别研究了BTOOH的晶体结构和热稳定性,并测试了其摩擦感度、撞击感度和静电感度。结果表明,BTOOH晶体属于单斜晶系,分子中含两分子配位水;其失水温度为123℃,放热分解峰温为245.49℃,显示了良好的热稳定性;BTOOH对撞击、摩擦和静电火花不敏感,感度均低于RDX。BTOOH制备工艺简单,可用于降温剂研究,具有较好的应用前景。 相似文献
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Zhiyong Zhou Wei Qin 《Journal of chemical technology and biotechnology (Oxford, Oxfordshire : 1986)》2011,86(4):492-496
BACKGROUND: To explore the extraction properties of aromatic acids produced in the oxidation of coal, the extraction equilibrium of phthalic acid (as a typical product) was studied using three solvents, 1‐octanol, 50% tributylphosphate (TBP)/kerosene, and 10% trialkylphosphine oxide (TRPO)/kerosene, and the feasibility of separating phthalic, [1,1′‐biphenyl]‐2,2′‐dicarboxylic and trimellitic acids is discussed. RESULTS: Phthalic acid extraction followed the sequence: 10% TRPO > 50% TBP > 1‐octanol, with recoveries from the TRPO and TBP systems being much larger than that for 1‐octanol. The stoichiometry of formation of the complexes of TBP and TRPO with phthalic acid was 1:1. The apparent extraction equilibrium constant for TRPO is much larger than that for TBP. The distribution coefficient of [1,1′‐biphenyl]‐2,2′‐dicarboxylic acid is much larger than that of the other two acids using 1‐octanol as the extractant and this acid could be removed by 1‐octanol from a mixture of the three acids. The extraction equilibrium correlations obtained for the individual acid component systems can be used to predict that of the acid mixture. CONCLUSION: The extent of phthalic acid extraction by the three solvents investigated is as follows: 10% TRPO > 50% TBP > 1‐octanol. The stoichiometry of the complex formation of TBP or TRPO and phthalic acid is 1:1, and the apparent extraction equilibrium constant for TRPO is much larger than that for TBP. 1‐octanol shows a good extractive selectivity for [1,1′‐biphenyl]‐2,2′‐dicarboxylic acid as compared with phthalic and trimellitic acids. Copyright © 2011 Society of Chemical Industry 相似文献
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Yehui Chen Liwen Yang Nianfa Yang Jingyi Yan Zhusheng Yang Jian Zhang 《Polymer Bulletin》2014,71(10):2507-2521
The synthesis and chiroptical properties of a novel optically active helical polymers, poly[(S)-6-acryloyl-2,2′-bisalkoxy-1,1′-binaphthyl] (poly-3), were reported. All the monomers readily underwent anionic polymerization to yield the polymers displaying optical rotations and Cotton effects in the UV–vis absorption region of side groups distinct to monomers (3) and the corresponding model compounds such as (S)-6-propionyl-2,2′-bisalkoxy-1,1′-binaphthyl (4) and (S)-6-heptanoyl-2,2′-bisalkoxy-1,1′-binaphthyl (5), implying the formation of main-chain chirality, most probable helicity. Their helical conformations were quite stable as revealed by the almost unchanged chiroptical properties measured at different temperatures. 相似文献