Mechanistic aspects of the Wolff-Kishner reaction. V. The cation effect on the reaction of benzophenone hydrazone in butyl carbitol and decyl alcohol

The rate of the Wolff-Kishner reaction of benzophenone hydrazone in butyl carbitol increases as the cation of the alkoxide base is varied in the order K>Na>Li>Mg. The replacement of butyl carbitol by 1-decanol also accelerates the reaction, and an additional increase is caused by the presence of crown ether. On the basis of changes in the activation parameters, it is concluded that the reactivity of the hydrazone anion increases as the contact ion pair becomes more fully solvated and dissociated.     

Reissert compound studies. Cyclization of N-(ω-chloroalkanoyl)reissert compounds

Treatment of 2-(4-chlorobutanoyl)- and 2-(5-chloropentanoyl)-1, 2-dihydroisoquinaldonitrile with sodium hydride gave rise to tricyclic benzoquinolizone and azepino[1,2-α]isoquinoline derivatives. A similar reaction was observed in the quinoline series. Several reactions of 1,2,3,4-tetrahydro-4-oxo-11bH-benzo[α]quinolizine-11b-carbonitrile are reported.     

Facile removal of tosyl chloride from tosylates using cellulosic materials,e.g., filter paper

Excess tosyl chloride used in the tosylation of alcohols is quickly and easily removed by reacting it with cellulosic materials, e.g., filter paper, and filtering.     

In Pursuit of a Competitive Target: Total Synthesis of the Antibiotic Kendomycin

Kendomycin is a novel polyketide having a unique quinone methide ansa structure and an impressive biological profile. Herein we provide a chronological overview of the synthetic work towards the title compound. Thus far, over a period of about eight years, eight groups worldwide have published on their synthetic efforts resulting in five total syntheses, one formal synthesis, and a number of fragment syntheses. Most approaches roughly mimic the biogenetic pathway, starting with an aromatic polyphenol subunit to which a polyketide chain is attached. Subsequent key steps include macrocyclization and the formation of the densely substituted tetrahydropyran ring, and then a late‐stage oxidation and lactol formation.     

Sodiation Of Hard Carbon: How Separating Enthalpy And Entropy Contributions Can Find Transitions Hidden In The Voltage Profile

Sodium-ion batteries (NIBs) utilize cheaper materials than lithium-ion batteries (LIBs) and can thus be used in larger scale applications. The preferred anode material is hard carbon, because sodium cannot be inserted into graphite. We apply experimental entropy profiling (EP), where the cell temperature is changed under open circuit conditions. EP has been used to characterize LIBs; here, we demonstrate the first application of EP to any NIB material. The voltage versus sodiation fraction curves (voltage profiles) of hard carbon lack clear features, consisting only of a slope and a plateau, making it difficult to clarify the structural features of hard carbon that could optimize cell performance. We find additional features through EP that are masked in the voltage profiles. We fit lattice gas models of hard carbon sodiation to experimental EP and system enthalpy, obtaining: 1. a theoretical maximum capacity, 2. interlayer versus pore filled sodium with state of charge.     

The fluoride ion effect in the reactions of singlet oxygen with enols

The fluoride ion effect in the reactions of enolic systems with singlet oxygen has been investigated. β-Dicarbonyl compounds yielded 1,2,3-tricarbonyl derivatives, some of which underwent further hydration, whereas α-diketones suffered oxidative decarboxylation to give open-chain aldehydo-acids or keto-acids.     

A total synthesis of (±)-cannabisativine

A synthesis of racemic cannabisativine is reported. Intramolecular opening of an $\text{erythro}$-acetoxy epoxide by a secondary amino group provided the side chain containing the desired stereochemistry.