Synthesis of 1,5-Benzodiazepines with Unusual Substitution Pattern from Chalcones Under Solvent-Free Microwave Irradiation Conditions

1,5-Benzodiazepines have been synthesized from the corresponding 2′-hydroxychalcones [1-(2-hydroxyphenyl)-3-aryl-2-propen-1-ones] and o-phenylenediamine, both in methanol, under reflux and under solvent-free microwave irradiation conditions on alumina. The latter method proved to be advantageous.     

Synthesis of 3-R-1-Acetyladamantanes by Substitution in 3-Chloro- and 3-Hydroxy-1-acetyladamantanes

Russian Journal of Organic Chemistry -     

A Lewis Acid Stabilized Ketenimine in an Unusual Variant of the Electrophilic Aromatic Substitution

Electrophilic aromatic substitution (EAS) can provide a straightforward approach to the efficient synthesis of functionalized complex aromatic molecules. In general, Lewis acids serve as a beneficial stimulus for the formation of a Wheland complex, the intermediate in the classical S_EAr mechanism of EAS, which is responsible for H/E (E=electrophile) substitution under formal H⁺ elimination. Herein, we report an unusual variant of EAS, in which a complex molecule such as the tricyanomethane, HC(CN)₃, is activated with a strong Lewis acid (B(C₆F₅)₃) to the point where it can finally be used in an EAS. However, the Lewis acid here causes the isomerization of the tricyanomethane to the ketenimine, HN=C=C(CN)₂, which in turn directly attacks the aromatic species in the EAS, with simultaneous proton migration of the aromatic proton to the imino group, so that no elimination occurs that is otherwise observed in the S_EAr mechanism. By this method, it is possible to build up amino-malononitrile-substituted aromatic compounds in one step.     

Reactivities of Carbonyl-Activated Angular and Vinyl Chlorine Substituents in Chloranyl-Cyclopentadiene Adduct Toward Nucleophiles. Synthesis of New 1,4-Benzoquinones Containing an Unusual Ortho Pattern of Substitution

Vinyl and angular chlorine atoms in chloranyl-cyclopentadiene adduct may be stepwise substituted by sulfur, nitrogen or oxygen nucleophiles to afford, after pyrolysis, highly substituted new quinones.     

4-Hydroxyacetophenone monooxygenase from Pseudomonas fluorescens ACB as an oxidative biocatalyst in the synthesis of optically active sulfoxides

Recombinant 4-hydroxyacetophenone monooxygenase (HAPMO) from Pseudomonas fluorescens ACB has been tested as a catalyst in sulfoxidation reactions on a set of aromatic sulfides. With a few exceptions, excellent enantioselectivities in the synthesis of chiral phenyl and benzyl sulfoxides were achieved. The bacterial Baeyer–Villiger monooxygenase was also shown to accept racemic sulfoxides, a prochiral diketone and an organoboron compound as substrates. This study demonstrates the great biocatalytic potential of this novel oxidative enzyme.     

Synthesis of 2-Hydroxy-3-Methyl-2-Cyclopentenone from Isoprene

Pyrolysis of the 1:1 isoprene-dichlorocarbene adduct and hydrolysis of the gem-dichlorocy-clopentene gave 3-methyl-2-cyclopentenone which was further processed to the title compound.     

Synthesis of 4-Pyridone-3-sulfate and an improved synthesis of 3-Hydroxy-4-Pyridone

An improved synthesis of 3-hydroxy-4-pyridone via an Elbs oxidation of 4-pyridone and isolation of 4-pyridone-3-sulfate is described.     

Nitration of alkaloids from carex parvae

The direct nitration of brevicolline, brevicarine, and methyl-, acetyl-, and hydroxybrevicarine with concentrated nitric acid gave 6- and 8-nitrobrevicolline and 6,8-dinitro derivatives of the enumerated compounds. 6-Nitroharman was obtained by oxidation of 6-nitrobrevicolline to 6-nitroharman-4-carboxylic acid and subsequent decarboxylation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 987–990, July, 1972.     

Synthesis of Unsaturated Ketones from 3-Hydroxy-1-adamantyl Methyl Ketone

The Claisen-Schmidt reaction between 3-hydroxy-1-adamantyl methyl ketone and aromatic aldehydes (benzaldehyde and 2-thiophenecarbaldehyde) in 2-propanol catalyzed by 50% aqueous potassium hydroxide affords 1-(3-hydroxy-1-adamantyl)-3-R-2-propen-1-ones. The reaction of 3-hydroxy-1-adamantyl methyl ketone with ethyl formate and sodium in benzene gives rise to sodium enolate of 1-(3-hydroxy-1- adamantyl)-3-hydroxy-2-propen-1-one. The latter compound treated with amine hydrochlorides in 50% aqueous alcohol furnishes 1-(3-hydroxy-1-adamantyl)-3-NRR'-amino-2-propen-1-ones.     

3-羟基-1-金刚烷甲基酮的合成

改进了沙格列汀中间体3-羟基-1-金刚烷甲基酮（1）的合成路线。以金刚烷甲酸（2）为起始原料,经二氯亚砜酰氯化后与N-氯代琥珀酰亚胺（NCS)反应制得3-氯-1-金刚烷甲酰氯（3）; 3依次经取代,脱羧和与碱反应合成1,其结构经¹H NMR, IR和MS(ESI)确证。采用星点设计-效应面法对1合成条件进行了优化。结果表明:在最佳反应条件[2 28 mmol, n(NCS)/n(2)/n(AIBN)=1/0.83/0.65,于65 ℃反应8 h]下,1收率70%。