Synthesis of 6,9-Dipropyl-1,4-Dioxaspiro[4.5] Deca-6,8-Diene-2,10-Dione and its Diels-Alder Reactions with Substituted Acetylenes

The title compound, a masked 3,6-di-n-propyl-o-benzoquinone, was synthesized from 3,6-di-n-propylcatechol in 82% yield. Its Diels-Alder reactions with methyl propiolate, phenylacetylene, 1-octyne, dimethyl acetylenedicarboxylate, diphenylacetylene and 3-hexyne were studied. The yields of the adducts were excellent except for the last two cases in which the unimolecular decomposition of the title compound to generate 3,6-di-n-propylcatechol methylene ether predominates. The regiochemistry of the adducts derived from monosubstituted acetylenes were determined by the correlation of ¹³C chemical shifts of the adducts and the corresponding bicyclo[2.2.2]octa-5,7-diene-2,3-diones obtained from the hydrolysis of the spirolactone ring of the Diels-Alder adducts. Photolysis of these α-diketones gave the corresponding aromatic compounds in high yields. These synthetic sequences provide an effective entry to bicyclo[2.2.2]octa-5,7-diene-2,3-diones and polysubstituted benzene derivatives.     

Challenges of structure determination of compound surfaces

Attention is drawn to challenges facing the structure determination of compound surfaces of growing complexity. Besides the questions of large unit cells and disorder, and of many independent atoms in the unit cells, one must address the determination of composition, compositional disorder and simultaneously coexisting structures. Of special concern is the issue of stability of complex and compound surfaces, and the resulting concerns about experimental surface preparation and reproducibility.     

Structural characterization of the epitaxially grown core–shell ZnTe/ZnMgTe nanowires

We report the method of the epitaxial growth of the core–shell ZnTe/ZnMgTe nanowires. The morphology and the crystal structure of several samples grown in different processes have been studied by scanning electron microscopy, high resolution transmission electron microscopy and X-ray diffraction methods. It was shown that the ZnMgTe shell growth was clearly epitaxial with a good crystal quality. The average lattice spacing of the ZnTe cores and ZnMgTe shells have been calculated and Mg content in the shells has been estimated. It was documented that growing the shell lattice mismatched to the core induces the strain in the core. The model of the strain creation mechanism has been proposed. The presence of a shell with a larger energy gap than that of the core results in a strong emission in the spectral region near the band edge.     

拓扑替康中三个有关物质的合成

采用易得的原料、简单的化学方法和方便的操作,设计了新的合成路线,制备了拓扑替康药物报批中的三种相关杂质。分别由拓扑替康盐酸盐(1)经游离、酯水解开环反应制备得到了拓扑替康羧酸钠盐(2),由拓扑替康(11)经正丙醇取代反应制备得到9-丙氧甲基-10-羟基喜树碱(4),以及由10-羟基喜树碱(5)经羟甲基化反应制备得到9-羟甲基-10-羟基喜树碱(3)。     

A facile approach to tricyclo[6.4.0.04,9]-dodecane framework

The unusual tricyclo[6.4.0.0^4.9]dodecane framework was constructed in eight linear steps in 13%overall yield.An innovative strategy accessing the framework from bicyclo[3.3.1]nonanes was employed.The key steps involve a Robinson annulation,a base induced decarboxylation and epimerization in a single step,and an intramolecular alkylation.     

Formation of Tetraacetal Oxa-Cages and Convex Oxa-Cages on Ozonolysis of Bicyclo[2.2.2] Octenes

Tetraacetal oxa-cage compounds 5a and 5b and convex oxa-cage compounds 7a and 8b are synthesized in a short sequence. Ozonolysis of endo adducts 2a and 2b in dichloromethane at ?78 °C followed by reduction with dimethylsulfide gave tetraacetal oxa-cages 5a and 5b in 35% yields respectively. Ozonolysis of 2a in dichloromethane at ?78 °C followed by treatment with triethylamine gave the convex oxa-cage 7a in 34% yield. These results support an acid-base proton transfer between the final ozonides and the base. The reasons that these oxa-cage compounds formed in low yields are discussed. The synthesis of tetraacetal oxa-cage 14, possessing aromatic substitutents directly on the skeleton of the oxa-cage, is accomplished.     

铕（Ⅲ）与HTTA及Phen类衍生物的三元固体配合物的红外及荧光光谱研究

合成了铕（Ⅲ）与２－噻吩甲酰三氟丙酮（ＨＴＴＡ）和１，１０－邻菲罗啉（Ｐｈｅｎ）及其衍生物的三元固体配合物，研究了它们的红外光谱和荧光光谱。     

Racemization of sulfinic esters with trichloroacetic anhydride

Both alkane- and arene-sulfinates undergo racemization and oxygen exchange reaction with trich-loroacetic anhydride. The rate of racemization of (?)menthyl (?)p-toluenesulfinate was found to be twice that of oxygen exchange, suggesting the reaction involves a Walden inversion. When reaction was carried out in benzene, the rate of racemization was found to be first order with respect to both sulfinic ester and trichloroacetic anhydride. The substituent effect is large (p = ?1.53) suggesting that the initial acylation is the rate-determining step. The rate of racemization was found to be retarded by the addition of perhaloacetic acid while very small catalytic effect of mercuric chloride was observed.     

Bindungsverh?ltnisse in Bicyclo(1.1.0)butanderivaten

Ohne Zusammenfassung

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Bonding conditions in bicyclo(1.1.0)butane derivatives