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1.
A cheap synthesis of the so‐called ‘decalin‐1,8‐diones’ started with the conjugate (1,4‐) addition of cyclohex‐2‐en‐1‐one derivatives to the γ‐position of the dilithium derivative (buta‐1,3‐diene‐1,1‐bis(olate)) of crotonic acid. Hydrogenation of these ‘1,4‐γ’ adducts and final cyclization afforded the enol tautomers of decalin‐1,8‐diones. Nucleophilic substitutions at these 3‐oxoenols by NH3 or primary amines created only monoamino products (namely, 3‐oxoenamines) whose reactions with OPCl3 yielded dihydro(1,3,2)oxazaphosphinin‐2‐one derivatives. The two regioisomers of a trimethyl‐3‐oxoenamine served as models for the constitutional assignments of the two rapidly interconverting (hence, individually NMR‐invisible), tautomeric trimethyl‐3‐oxoenols. Such methyl substitutions served to break the ‘pretended’ symmetry of ‘decalin‐1,8‐dione’. Hydrazine and 3‐oxoenols furnished oxygen‐free indazole derivatives whose N?H bonds exchanged with t1/2=ca. 0.00035 s at ca. ?58(9) °C. 相似文献
2.
针对大气垂直方向上消光系数分布不均匀难以用传统方法直接测量垂直能见度的问题,提出了一种基于激光雷达探测垂直能见度的计算方法。根据大气辐射传输基本原理,借助于辐射传输方程,推导出了垂直能见度的计算公式;然后利用激光雷达原理方程和Klett算法反演出大气垂直方向上的消光系数分布,基于此提出了垂直能见度的迭代算法。最后,利用灰色模型GM(1,1)和批统计算法,对激光雷达反演得到的后向散射系数进行了评估,给出了误差置信区间为(0.760±0.339)×10^-4(srad·km)^-1。结果表明,该方法是一种特别有效的计算垂直能见度的方法,符合探测的基本需求,且误差小精度高。 相似文献
3.
Ronald C. Crouch Jeffrey G. Raab Marius Pelmuş Evgeny Tischenko Michael Frey Alexei V. Buevich Mikhail Reibarkh R. Thomas Williamson Gary E. Martin 《Magnetic resonance in chemistry : MRC》2022,60(2):210-220
Modification of the recently reported 19F-detected 1,1-ADEQUATE experiment that incorporates dual-optimization to selectively invert a wide range of 1JCC correlations in a 1,n-ADEQUATE experiment is reported. Parameters for the dual-optimization segment of the pulse sequence were modified to accommodate the increased size of 1JCC homonuclear coupling constants of poly- and perfluorinated molecules relative to protonated molecules to allow broadband inversion of the 1JCC correlations. The observation and utility of isotope shifts are reported for the first time for 1,1- and 1,n-ADEQUATE correlations. 相似文献
4.
Reversal Circularly Polarized Luminescence of AIE‐Active Chiral Binaphthyl Molecules from Solution to Aggregation 下载免费PDF全文
Yuan Sheng Dong Shen Wenjie Zhang Prof. Hongxing Zhang Prof. Chengjian Zhu Prof. Yixiang Cheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(38):13196-13200
Four aggregation‐induced emission (AIE)‐active chiral binaphthyl‐based molecules, (R/S)‐ 1 and (R/S)‐ 2 , were designed and synthesized. Interestingly, all of them can exhibit reversal circularly polarized luminescence (CPL) signals from solution to aggregation, which could be attributed to the different dihedral angle of binaphthyl units from cis‐conformation in pure THF solution to trans‐conformation in THF/water mixtures. 相似文献
5.
In this paper, (vapour + liquid) equilibrium (VLE) for the {1,1-difluoroethane (R152a) + 1,1,1,3,3-pentafluoropropane (R245fa)} system was determined by a static-analytical method at T = (323.150 to 353.150) K. Values of the VLE were correlated by the Peng–Robison equation of state (PR EoS) using two different models, the van der Waals (vdWs) mixing rule and the Huron–Vidal (HV) mixing rule involving the non-random two-liquid (NRTL) activity coefficient model. The correlated results show good agreement with the experimental values. For the two models, the maximum average absolute deviations of the vapour phase mole fraction are 0.0034 and 0.0035, respectively. 相似文献
6.
Hyun‐Chul Kim Ja‐Min Gu Seong Huh Chul‐Hyun Yo Youngmee Kim 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(10):929-935
Two new one‐dimensional CuII coordination polymers (CPs) containing the C2h‐symmetric terphenyl‐based dicarboxylate linker 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate (3,3′‐TPDC), namely catena‐poly[[bis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ4O,O′:O′′:O′′′] monohydrate], {[Cu(C20H12O4)(C2H7N)2]·H2O}n, (I), and catena‐poly[[aquabis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ2O3:O3′] monohydrate], {[Cu(C20H12O4)(C2H7N)2(H2O)]·H2O}n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4‐diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X‐ray crystallography. The 3,3′‐TPDC bridging ligands coordinate the CuII ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one‐dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one‐dimensional coordination polymer chains, forming a two‐dimensional network in (I) and a three‐dimensional network in (II). 相似文献
7.
以1,1′-二羟基-5,5′-联四唑(H_2BTO)为配体,镧系金属离子作为金属中心,采用溶剂热法制备了5种金属配合物:[La_2(BTO)_3(H_2O)_8]·2H_2O (1)、[Ce_2(BTO)_3(H_2O)_8]·2H_2O (2)、[Pr_2(BTO)_3(H_2O)_8]·2H_2O (3)、[Sm_2(BTO)_3(H_2O)_8]·2H_2O (4)和[Nd_2(BTO)_3(DMF)_4]·6H_2O (5)。通过单晶X射线衍射和元素分析对5种配合物的结构进行了表征。结果表明,5种配合物均属于单斜晶系,P2_1/n空间群。利用差示扫描量热法研究了配合物1~4的热稳定性,采用Kissinger法和Ozawa法分别计算了其热分解动力学参数。 相似文献
8.
Kukhtin-Ramirez反应是有机化学中一类重要的极性反转反应.利用三价磷的还原性对α-羰基酮化合物进行极性反转,所生成的Kukhtin-Ramirez活性中间体在诸多转化中都展现出了其作为1,1-偶极子的化学性质.近年来关于该活性中间体的反应研究主要包括:极性X—H键插入反应、还原性加成反应、形式[2+1]环加成反应、形式[4+1]环加成反应、形式[4+2]环加成反应.这些转化为一些重要的多官能团化合成中间体及结构复杂的环状化合物提供了高效简洁的合成方法,凸显了Kukhtin-Ramirez极性反转反应在有机合成中的重要性. 相似文献
9.
10.
GARCH(1,1)模型的稳健估计比较及应用 总被引:1,自引:0,他引:1
首先阐述了GARCH(1,1)模型稳健估计的构造方法,然后在模型有无异常值扩散效应约束和异常值比例不同的情况下,比较了传统QMLE估计和多种稳健M估计的表现,结果表明:在数据无异常值下,QMLE估计较优;随着异常值比例增加,稳健Andrew估计表现更好;模型施加异常值扩散效应约束对估计有一定改善但不显著.最后选取波动程度不同的两个阶段沪深300指数的收益率,用模型拟合进行了实例比较,在波动程度较大时,Andrew估计效果较优,在波动相对平稳时,LAD估计较优. 相似文献