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31.
Xiu-Rong Huang Yu-Mei Zhang Ting-Biao Wan Piao Zhang Xiu-Xiu Zhang Fang-Ming Wang Defeng Xu Mei-Hua Shen Hua-Dong Xu 《Tetrahedron》2019,75(45):130336
Functionalized 1,2-oxazinanes are interesting and valuable heterocycles with potential applications in synthetic and medicinal chemistry. A straightforward strategy for quick access to unprecedented trans-4-hydroxyl-5-azido/cyano/amino 1,2-oxazinanes are developed: N-COR 3,6-dihydro- 1,2-oxazine oxides are prepared with ease from related dihydro- 1,2-oxazines and opened by nucleophiles TMSN3, TMSCN and aryl/alkyl amines. Appropriate Lewis acid catalysts are found playing a vital role for both reaction rate and regioselectivity. The N-COR group can be removed under mild conditions to provide highly desirable NH 1,2-oxazinanes inaccessible via previous methods. 相似文献
32.
合成了一种新型的,能在含水介质中比色荧光双通道单一选择性识别CN-的传感器分子1-羟基萘甲叉酰肼乙基-3-羟基萘甲叉酰肼甲基苯并咪唑溴鎓盐(J1)。 在J1的DMSO/H2O (体积比3:2)HEPES 的缓冲体系(pH=7.2)中分别加入F-、Cl-、Br-、I-、AcO-、HSO4-、ClO4-、H2PO4-、SCN-和CN-等阴离子后,只有CN-的加入会使得溶液颜色发生明显的变化,由无色变为深黄色。 相应地在J1的DMSO/H2O (体积比4:1)HEPES的缓冲体系(pH=7.2)中加入CN-,溶液发出明亮的黄色荧光。 这一识别过程,不会受到其它阴离子的干扰。 紫外-可见光谱的最低检测限为1.57×10-7 mol/L,检测线性范围为3.875×10-4~2.15×10-2 mol/L。 荧光光谱的最低检测限为4.63×10-6 mol/L,检测线性范围为0.8×10-4~1.60×10-3 mol/L。 此结果表明,J1是一种良好的用于识别 CN-的化学传感器,在含水介质中对CN-具有选择性好、灵敏度高以及抗干扰性强的识别性能。 与此同时,基于J1对于CN-的高选择性识别我们制备了CN-的检测试纸,该试纸能够方便、快捷、准确地检测水中的CN-。 相似文献
33.
Benjamin Schmidt Benjamin Schrder Karsten Sonnenberg Simon Steinhauer Sebastian Riedel 《Angewandte Chemie (International ed. in English)》2019,58(30):10340-10344
Pseudohalogens are defined as molecular entities that resemble the halogens in their chemistry. While our understanding of polyhalogen chemistry has increased over the last years, research on polypseudohalogen compounds is lacking. The pseudohalogen BrCN possesses a highly pronounced σ‐hole at the bromine side of the molecule, inducing strong halogen bonding. This allows the synthesis and characterization of new polypseudohalogen anions, as shown by the single‐crystal X‐ray diffraction of [PNP][Br(BrCN)] and [PNP][Br(BrCN)3]. Both the nearly linear anion [Br(BrCN)]? and the distorted pyramidal anion [Br(BrCN)3]? were characterized by Raman spectroscopy and quantum‐chemical calculations. The behavior of the polypseudohalogen compounds in solution and as room‐temperature ionic liquids (RT‐ILs) using the [NBu4]+ cation was studied by 13C and 15N NMR spectroscopy. These types of ILs are capable of dissolving elemental gold and offer themselves as promising compounds in metal recycling. 相似文献
34.
新型的承载双金属氰化物络合催化剂 总被引:1,自引:0,他引:1
用双金属氰化物(DMC)络合催化剂可制得相对分子质量高、相对分子质量分布窄和不饱和度低的聚醚多元醇。为提高DMC催化剂的利用率,降低催化剂和聚醚的生产成本,国外开发了承载的DMC催化剂。它不仅可简化聚醚的后处理工艺,而且使聚醚的连续化大规模生产得以实现,因此代表了DMC催化剂的一个重要发展方向。 相似文献
35.
The quadratic, cubic and semi-diagonal quartic force field of ethyl cyanide has been calculated at the B3LYP level of theory employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. This structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quadruple-ζ quality and a core correlation correction. The empirical structures are also determined and their accuracy is discussed. The potential barrier V3 hindering internal rotation of the methyl group has been calculated from 23 rotational transitions of CH3CH2C15N which were found split into doublets, giving V3 = 3074(27) cal mol−1. 相似文献
36.
Potassium phthalimide was found to be a highly effective and easily accessible organocatalyst for the cyanosilylation of various carbonyl compounds under extremely mild conditions. The corresponding cyanohydrin trimethylsilyl ethers were obtained in high to quantitative yields in solvent-free conditions at room temperature using 2.5 mol% catalyst loading. 相似文献
37.
《Magnetic resonance in chemistry : MRC》2002,40(11):716-722
205Tl longitudinal relaxation rate measurements were performed on several thallium(III) complexes with the composition Tl(OH)n(H2O)6?n(3?n)+ (n = 1,2), Tl(Cl)n(H2O)m?n(3?n)+, Tl(Br)n(H2O)m?n(3?n)+ (m = 6 for n = 1–2, m = 5 for n = 3, m = 4 for n = 4), Tl(CN)n(H2O)m?n(3?n)+ (m = 6 for n = 1–2, m = 4 for n = 3–4) in aqueous solution, at different magnetic fields and temperatures. 13C and 2D isotopic labelling and 1H decoupling experiments showed that the contribution of the dipolar relaxation path is negligible. The less symmetric lower complexes (n < 4) had faster relaxation rate dominantly via chemical shift anisotropy contribution which depended on the applied magnetic field: T1 values are between 20 and 100 ms at 9.4 T and the shift anisotropy is Δσ = 1000–2000 ppm. The tetrahedral complexes, n = 4, relax slower; their T1 is longer than 1 s and the spin–rotation mechanism is probably the dominant relaxation path as showed by a temperature dependence study. In the case of the TlCl4? complex, presumably a trace amount of TlCl52? causes a large CSA contribution, 300 ppm. Since the geometry and the bond length for the complexes in solution are known from EXAFS data, it was possible to establish a correlation between the CSA parameter and the symmetry of the complexes. The relaxation behaviour of the Tl–bromo complexes is not in accordance with any known relaxation mechanism. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
38.
The response characteristics of the solid state cyanide ion selective electrode towards some benzylnitriles are investigated. In 10M KOH solution, the electrode exhibits nearly Nernstian response over the concentration range of 10–2 to 10–4
M of various substituted benzylnitriles with an anionic slope of 53–59 mV/concentration decade. The response time varies from 10 to 20 min depending on both the nature of the substituent group and the concentration of the nitrile compound. Direct potentiometric measurement of some nitrile compounds at the concentration level of 0.01 to 1 mg/ml shows an average recovery of 98.2% and a mean standard deviation of 2.3%. Many nitrogen functional groups do not interfere. 相似文献
39.
A straightforward and efficient method has been developed for the synthesis of α‐aminonitriles by combining aldehydes, amines and trimethylsilyl cyanide in the presence of a catalytic amount of thallium(III) chloride tetrahydrate (1 mol%) under solvent‐free conditions at room temperature. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
40.
We wish to present herein a simple one-pot synthesis of 2,5-disubstituted oxazoles, starting from benzyl halides and acyl chlorides. The in situ formation of isocyanides, followed by the addition of an acyl chloride in the presence of a base leads to the desired oxazoles in good yields. 相似文献