Hydrocarbomethoxylation of 1-hexene with formic acid and methanol under conditions of phosphoric acid catalysis

Conclusions When the hydrocarbomethoxylation of 1-hexene with formic acid is run at atmospheric pressure and temperatures close to room temperature, in the presence of conc. H₃PO₄, an increase in the relative amount of the latter, as well as an increase in the reaction temperature in the investigated range, both favor an increase in the yields of the methyl esters of the C₇ acids, in particular, those containing two methyl groups on the quaternary carbon atom in the -position. An increase in the relative amount of formic acid also favors an increase in the amounts of these esters in the obtained mixtures of esters.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1116–1118, May, 1971.     

Mechanism of the decomposition of cumenyl hydroperoxide under the influence of complexes of divalent copper with o-phenanthroline

Russian Chemical Bulletin -     

Reactions of azirines with sulfur nucleophiles. 2. Reactions of 2H-azirine with β,γ-dihydroxy thiols and β-dithiols. a new route to the synthesis of cyclic sulfides

The reaction of 2H-azirine with a number of dihydroxy thiols and dithiols leads to aziridin-2-yl alkyl sulfides. The latter readily isomerize to cyclic sulfides the size of the ring of which is determined by the length of the alkyl sulfide chain.For Communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 623–627, May, 1985.     

Selective suppression of some radical reactions by iron pentacarbonyl

Conclusions On the example of the homolytic reaction of methallyl chloride with CCl₄ it was found that iron pentacarbonyl in catalytic amounts can selectively suppress the radical process involving chlorine atoms, and at the same time it catalyzes the chain reaction with trichloromethyl radicals, which act as carriers of the kinetic chain.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2320–2322, October, 1972.     

‘Sacrificial’ supramolecular assembly and pressure-induced polymerization: toward sequence-defined functionalized nanothreads

Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence of noncovalent interactions in materials design. Herein, we illustrate the utility of ‘sacrificial’ aryl-perfluoroaryl supramolecular synthons to synthesize sp³-hybridized nanothreads from sp²-enriched reactants. Our strategy features A–B reactant pairs in the form of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous –OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto–enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.

Supramolecular synthons are exploited to synthesize –OH functionalized sp³-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal.      

Bidentate ligands formed by self-assembly

A novel supramolecular strategy to prepare bidentate ligands via the assembly of functionalised monomeric ligands on a dimeric zinc(II) porphyrin template is presented; the assembled bidentate ligands show chelating behaviour and their rhodium complexes display enhanced selectivity in the hydroformylation compared to the non-template analogue.