硅氮化合物的结构与水解稳定性的关系

采用硅氮化合物本体与水蒸汽直接作用的方法,研究了一系列硅氮化合物的结构与水解稳定性之间的关系.结果表明,空间位阻越大则硅氮化合物水解稳定性越好,环张力对硅氮烷的水解稳定性有一定的影响,但空间位阻的作用更为显著.带有苯基的环二硅氮烷、六苯基环三硅氮烷和含硅氮键的高分子聚合物具有较大的空间位阻,因此水解稳定性非常好.     

1,1,3,3-四(全氟己基乙基)二锡氧烷二聚体在环氧化合物开环反应中的催化作用

采用氟碳-有机溶剂两相催化体系,考察了1,1,3,3-四(全氟己基乙基)二锡氧烷二聚体(1)在环氧化合物开环反应中的催化作用.结果表明,催化剂(1)在氟碳-有机溶剂两相体系中使环氧苯乙烯和甲醇的开环反应产率高达95%,¹³CNMR谱表明,开环反应的区域选择性为100%.在氟碳-有机溶剂两相催化体系中以一锅法制备了3-苯基丙酸2-甲氧基-2-苯乙醇酯,收率高,方法简便,催化剂几乎可以定量回收循环使用.     

Efficient Preparation of γ-Hydroxynitriles via Nitrile Enolate-Epoxide Reactions: Scope and Diastereoselectivity

The nucleophilic opening of epoxides by nitrile enolates using an efficient, convenient protocol is described. The diastereoselectivity of this reaction was explored and found to give syn:anti ratios ranging from 1.1:1.0 to 4.8:1.0.

     

Synthesis of orthogonally protected azepane β-amino ester enantiomers

A simple and convenient route is presented for the preparation of regio- and stereoisomers of novel azepane β-amino esters, starting from bicyclic β-lactam isomers. The synthetic procedure consists of dihydroxylation of the olefinic bond of the alicyclic amino esters, followed by NaIO₄-mediated cleavage of the diol intermediate and reductive ring closure, which furnishes novel regioisomeric 5-aminoazepane-4-carboxylate and 3-aminoazepane-4-carboxylates. This method also allows the preparation of amino esters with an azepane skeleton in enantiomerically pure form.     

MBAMT,a new locating and chelating agen in TLC and ring colorimetric determination of Cu(II), Co(II), Ni(II), Pd(II), Pt(IV), and Rh(III)

Summary Synthesis of MBAMT (3-methyl-4-benzylideneamino-5-mercapto-1,2,4-triazole) and its IR and NMR spectral data are reported. The high stability of the characteristically coloured chelates with Cu(II), Co(II), Ni(II), Pd(II), Pt(IV) and Rh(III) has been made the basis for their efficient ascending TLC separations on silica gel G layers, when present together. Results of four different solvent systems are included to assess efficient resolution of the chelates along with their limits of identification and separation. TLC separations, followed by the ring colorimetric determination of the six metal ions (as ternary mixtures) are tabulated.MBAMT=3-methyl-4-benzylideneamino-5-mercapto-1,2,4-triazole.     

High sensitivity CW-Cavity Ring Down Spectroscopy of N2O near 1.5 μm (II)

We present the second part of the investigation of the high sensitivity absorption spectrum of nitrous oxide by CW-Cavity Ring Down Spectroscopy near 1.5 μm. In a first paper [A.W. Liu, S. Kassi, P. Malara, D. Romanini, V.I. Perevalov, S.A. Tashkun, S.M. Hu, A. Campargue, J. Mol. Spectrosc. 244 (2007) 33-47] devoted to the 6000-6833 cm⁻¹ region, more than 6000 line positions of five isotopologues (¹⁴N₂¹⁶O, ¹⁵N¹⁴N¹⁶O, ¹⁴N¹⁵N¹⁶O, ¹⁴N₂¹⁷O, and ¹⁴N₂¹⁸O), were rovibrationally assigned to a total of 68 bands. The achieved noise equivalent absorption (α_min ∼ 2 × 10⁻¹⁰ cm⁻¹) allowed for the detection of lines with intensity weaker than 2 × 10⁻²⁹ cm/molecule. In this contribution, the investigated region was extended down to 5905 cm⁻¹ and additional recordings allowed accessing small spectral sections uncovered in our preceding recordings. A deeper analysis based on the predictions of the effective Hamiltonian model has allowed assigning a total of 3149 transitions and lowering the percentage of lines left unassigned from 51% to 28%. It led to the analysis of 35, 6, 7, and 6 bands for the ¹⁴N₂¹⁶O, ¹⁵N¹⁴N¹⁶O, ¹⁴N¹⁵N¹⁶O, and ¹⁴N₂¹⁸O isotopologues, respectively. Forty-two of these 54 bands are newly observed, while the rotational analysis of the twelve others is significantly extended and improved. Most of the bands were found unperturbed and their line positions could be reproduced within the experimental uncertainty (about 1 × 10⁻³ cm⁻¹). The corresponding spectroscopic parameters are reported. Local rovibrational perturbations induced by either intrapolyad or interpolyad couplings were found to affect five hot bands of ¹⁴N₂¹⁶O. Their detailed analysis is presented.     

Total Synthesis of (±)‐Infuscol A and (±)‐Cuprenenol

Abstract

Total synthesis of the nonaromatic cuparenoid sesquiterpenes (±)‐infuscol A and cuprenenol, and (±)‐infuscol B and neocuprenenol isolated from the Japanese liverwort Jungermannia infusca has been accomplished. Two ring‐closing metathesis reaction based strategies have been developed for the generation of the key intermediate of the sequence.     

A total synthesis of 11-O-methyldebenzoyltashironin

A concise total synthesis of 11-O-methyldebenzoyltashironin is reported in which oxidative dearomatization-IMDA-RCM triad constitutes the key ring forming steps, while an unorthodox DIBAL-H mediated stereo- and regioselective reductive epoxide openings and implementation of the vinyl bromide-carbonyl equivalency concept were pivotal to the success of this endeavor.     

Hydrolytic Ring Opening Reactions of Pyromellitic Dianhydride for Divalent Transition Metal Carboxylate Complexes

The hydrolytic ring opening reactions of pyromellitic dianhydride is an effective method to prepare transition metal carboxylate complexes. In this paper, two dinuclear complexes [Ni₂(2,2′‐bipy)₂(btec)(H₂O)₆] · 2H₂O ( 1 ) and [Cd₂ (phen)₄(H₂O)₂(H₂btec)] · H₂btec · 2H₂O ( 2 ) (H₄btec = 1,2,4,5‐benzenetetracarboxylic acid, phen = 1,10‐phenanthroline, and 2,2′‐bipy = 2,2′‐bipyridine) were synthesized by slow diffusion methods and their structures were determined byX‐ray structure analysis. In both structures metal atoms are in distorted octahedral environments and they are linked by bis‐monodentately coordinated 1,2,4,5‐benzentetracarboxylate ligands as bridging units. The crystalline compounds, which are insoluble in water as well as common organic solvents, have been characterized in the solid‐state by elemental analysis, thermogravimetric analysis, IR, and diffuse reflectance UV/Visspectroscopy. Moreover, the study of the physical properties of complex 2 demonstrates that it exhibits blue fluorescence emission in the solid state at room temperature.