Kinetics and mechanism of diphenylamine synthesis by the condensation of aniline with oxygen-containing compounds

The condensation of aniline and cyclohexanol (cyclohexanone) yielding intermediates and the subsequent dehydrogenation of these intermediates into diphenylamine have been studied. The mechanism of diphenylamine synthesis is substantiated. The kinetics of diphenylamine synthesis from aniline and cyclohexanol over a NiSnMg catalyst has been studied. A kinetic model in terms of the conversion of strongly chemisorbed species has been developed. The rate constants of diphenylamine synthesis at 260–300°C have been determined, which are consistent with the observed regularities. The kinetic model can be used in the determination of optimal synthetic conditions and in the design of a reactor for diphenylamine synthesis from aniline and cyclohexanol. Conditions have been found under which diphenylamine synthesis occurs at a high rate of up to 1 kg/(1h), with high selectivity, and with a high yield of up to 95%.     

Synthesemethoden für keramische Materialien. Hochtechnologiewerkstoffe

The new developments in the field of gas phase synthesis, synthesis from the condensed phases and solid‐state synthesis allowing for the fabrication of new ceramic materials for diverse technical applications have been reviewed. The Flame Spray Pyrolysis, aqueous and non‐aqueous sol‐gel techniques, hydro‐ and solvothermal methods, polymer pyrolysis route and high pressure techniques have been considered as synthesis methods with great technical potential.     

A Stereoselective Total Synthesis of Xyolide,a Natural Bioactive Nonenolide

A stereoselective total synthesis of xyolide, a naturally occurring bioactive nonenolide, has been accomplished. The acid fragment of the molecule has been prepared from D ‐mannitol and the alcohol fragment from (2Z)‐but‐2‐ene‐1,4‐diol. The synthesis involves the coupling of these two fragments using the Yamaguchi esterification protocol, followed by intramolecular ring‐closing methathesis. The diastereoisomeric alcohol fragment has also been utilized in this synthesis by employing the Mitsunobu esterification.     

Studies towards the synthesis of epothilone A via organoboranes

Studies towards the synthesis of epothilone A via organoboranes have been described. A modified procedure for the large-scale preparation of B-gamma,gamma-dimethylallyldiisopinocampheylborane from prenyl alcohol has been developed. This reagent, upon reaction with various aldehydes, provides the corresponding alpha,alpha-dimethylhomoallylic alcohols in high enantioselectivities. The application of this reagent for the synthesis of the C1-C6 subunit of epothilone has been demonstrated. Alternatively, inter- and intramolecular asymmetric reduction protocols have also been utilized for the synthesis of the C1-C6 subunit of epothilone A. The synthesis of the C7-C21 fragment of epothilone A involving asymmetric alkoxyallyl- and crotylboration using alpha-pinene-derived reagents has also been described.     

Synthesis of (+/-)-epi-stegobinone utilizing silacyclopropanes as synthetic intermediates

The synthesis of (+/-)-1'-epi-stegobinone has been accomplished in ten steps and 17% overall yield from a recently reported silacyclopropane-derived diol. All stereocenters of the final product were established relative to the stereochemistry of the initial silacyclopropane. This synthesis represents the first time silacyclopropane reactivity has been employed in a target-directed synthesis.     

Synthesis of polyhydroxycyclohexanes and relatives from (-)-quinic acid

An efficient and versatile strategy for the synthesis of polyhydroxycyclohexanes and related compounds 3-6 is reported. The successful synthesis of these analogues has been achieved from a common intermediate, quinic acid derived lactone 2, rapidly accessible from cheap and commercially available (-)-quinic acid (1) as a chiral template. A practical route involving stereocontrolled epoxide formation and hydrolysis has been developed for the synthesis of 2,3-trans analogues 3 and 4. The preparation of the 2,3-cis analogues 5 and 6 has been realized by diasteroselective oxidation of a 5,6-double bond.     

Direct catalytic asymmetric synthesis of cyclic aminals from aldehydes

A highly enantioselective Br?nsted acid catalyzed direct synthesis of cyclic aminals from aldehydes has been developed. The methodology has been applied to the first asymmetric synthesis of several antihypertensive aminal drugs including (R)-Thiabutazide.     

“4,7-lactams”, intermediates for penems synthesis. II. Total synthesis of (+)-2,2-dimethyl-9-oxo-3-oxa-6-thia-1-azabicyclo [5.2.01,7]nonane

The total synthesis of chiral “4,7-lactam” $\text{4}$ has been accomplished starting from 4-acetoxyazetidinone. An independent route from methyl penicillanate has been used to test the efficiency of the foregoing synthesis.     

微波辅助组合合成的研究进展

微波辅助组合合成技术是近年来发展起来的一种新的制备化合物库的组合化学技术, 它不仅可以克服传统固相组合合成技术以及液相组合合成技术无法提高产物收率的不足, 而且利用该技术所制得的化合物库中对应的是高纯度的单一化合物, 采用高通量筛选技术可以快速直接地确定高活性结构, 极大地提高了新药开发的效率. 主要就近年来微波辅助组合合成技术的研究进展情况进行介绍, 内容包括固相组合合成、基于聚合物支载的催化剂的组合合成、液相组合合成、氟相组合合成以及组合平行合成等.     

Total synthesis of pyridovericin: studies toward the biomimetic synthesis of pyridomacrolidin

[reaction: see text] The total synthesis of the novel metabolite pyridovericin 1 is reported. The synthesis of this key intermediate in our proposed biomimetic synthesis of pyridomacrolidin 2 has been accomplished in good yield from readily available 2,4-dihydroxypyridine.     

Synthesis of ellipticine: a radical cascade protocol to aryl- and heteroaryl-annulated[b]carbazoles

[reaction: see text] Imidoyl selanides, synthesized from amides, have been used as radical precursors of imidoyl radicals in cascade reactions. The novel radical cascade has been developed for the simple synthesis of the medicinally important aryl-annulated[b]carbazoles. The protocol has been exemplified with the high-yielding total synthesis of the anticancer alkaloid ellipticine.     

Studies directed towards the total synthesis of anthracycline antibiotics

At present anthracycline antibiotics have proven to be the most exciting agents in cancer chemotherapy. Both adriamycin and daunomycin are proven to be effective against a variety of human tumour cells, despite their cardiotoxicity. However, some synthetic analogues, such as 4-demethoxydaunomycin, are shown to be better therapeutic ratios compared to adriamycin or daunomycin. Various approaches have been successfully made for the total synthesis of (±) 4-demethoxydaunomycinone, the aglycone of (±) 4=demethoxydaunomycin, starting from benzoquinone, napthalene or anthraquinone precursors. Finally an elegant approach for the stereoconvergent synthesis of (+) 4-demethoxydaunomycinone has been worked out. New methods involving both Diels-Alder and Friedal-Crafts acylation, have been developed for the total synthesis of daunomycinone and 11-deoxydaunomycinone. The synthesis of L-daunosamine, the amino sugar unit present in the antitumor anthracyclines has been successfully elaborated starting either from D-glucose or D-glucosamine.     

Clean and efficient synthesis of O-silylcarbamates and ureas in supercritical carbon dioxide

The synthesis of a family of O-silylcarbamates from the corresponding silylamines has been achieved simply by heating the silylamine in supercritical carbon dioxide (scCO2), and these O-silylcarbamates have been shown to be effective precursors for the synthesis of a range of symmetrical and unsymmetrical ureas.     

Catalytic synthesis of C-alkylimidazoles over platinum-alumina catalysts

The synthesis of C-alkylimidazoles from 1,2-diamines and carboxylic acids over bifunctional platinum—alumina catalysts has been studied. It has been shown that this method is effective for the synthesis of 2-alkyl and 2,4-dialkylimidazoles including imidazoles with long-chain alkyls. The effect of the reaction temperature, space velocity of the flow of the raw materials, and dilution by hydrogen on the yield of product has been examined for the example of the synthesis of 2-methylimidazole from ethylenediamine and acetic acid, and the stability of the catalyst in continuous reaction cycles with intermediate oxidative regeneration has been studied. The composition of the accompanying products has been established and a mechanism proposed for their formation.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 932–940, April, 1992.     

Synthesis of diazoketones derived from α-amino acids; problem of side reactions

Optimum conditions of synthesis of eight diazoketones derived from optically active N-(t-butyloxycarbonyl)- and N-benzyloxycarbonylamino acids have been described. The problem of formation of by-products during Arndt-Eistert synthesis of β-homoamino acids at the stage of reaction of mixed anhydride with a weak nucleophile-diazomethane - has been discussed.     

Stereoselective total synthesis of (+)-synargentolide A

The stereoselective synthesis of synargentolide A, a polyhydroxy δ-lactone, has been accomplished from tartaric acid. The key steps in the synthesis involve Keck and Brown allylations and ring closing metathesis.     

Efficient synthesis of ningalin C

[reaction: see text] A concise and efficient synthesis of the permethyl derivative of the marine alkaloid ningalin C (2) has been accomplished. The key step involves the formation of a pyrrolinone from an aminoquinone in one pot. An efficient route for the synthesis of the key aminoquinone has also been developed.     

α－烯丙基甘油醚的合成新方法

在路易斯酸催化下，烯丙醇和环氧氯丙烷经加成、环化和水解后得到标题化合物，该法比文献报道的甘油－氯丙烯法产率提高约１０％。     

Facile synthesis of @-tide beta-strand peptidomimetics: improved assembly in solution and on solid phase

The synthesis of @-tide beta-strand peptidomimetics has been improved such that oligomers now can be obtained from solution- and solid-phase synthesis protocols approaching the efficiency and flexibility of peptide chemistry. These methods enable the synthesis of @-tide oligomers with a variety of amino acids and with lengths up to 13 units. [reaction: see text]     

Synthesis and absolute configuration of three natural ent-halimanolides with biological activity

The first three natural ent-halimanolides known until now have been synthesized from ent-halimic acid. Their structure have been confirmed as well as their absolute configurations established. Bestmann methodology has been used for the synthesis of butenolides and for the γ-hydroxybutenolides synthesis the Boukouvalas method has been employed. Biological testing has been carried out on these compounds.