Reaction of Methyl Diazoacetate with Amines Catalyzed by Ru<Subscript>2</Subscript>(OAc)<Subscript>4</Subscript>Cl

Reactions of primary and secondary amines with methyl diazoacetate in the presence of Ru₂(OAc)₄Cl gave the corresponding N-substituted glycine methyl esters in almost quantitative yield. Catalytic decomposition of methyl diazoacetate generates methoxycarbonylcarbene which is inserted into the N-H bond of amines with high regioselectivity.     

Sulfur ylides. 12. Optically active keto stabilized sulfur ylide obtained from L-proline: synthesis and study

Optically active keto stabilized sulfur ylide was synthesized from L-proline. The reactions of the ylide with methyl acrylate and methyl vinyl ketone afforded 1,2-disubstituted cyclopropanes. In the case of acrylonitrile, a mixture of 1,2- and 1,1-disubstituted cyclopropanes was obtained. Acylation of the ylide with acetic anhydride gave twice stabilized sulfur ylide.     

Sulfur ylides. 10. Modified method for the synthesis of pyrrolizine- and indolizinediones

A modified method for the synthesis of derivatives of pyrrolizinedione and indolizinedione was proposed. The method is based on the intramolecular cyclization of keto-stabilized sulfur ylides generated in situ from diazo ketones and Me₂S in the presence of Rh₂(OAc)₄.     

Catalytic Cyclopropanation of Ricinolic Acid Derivatives with Diazomethane

The reaction of ricinolic acid methyl ester with diazomethane in the presence of Co(BF₄)₂·6H₂Oresults in selective methylation of the hydroxy group. Methyl (2Z'12R)-12-acetoxy-9-octadecenoate reactswith diazomethane in the presence of Pd(acac)₂, leading to formation of a mixture of cis-cyclopropanated(9S'10S'12R)-, (9R'10R'12R)-diastereoisomers at a ratio of 3:2 (overall yield 73%). Under similarconditions methyl (9Z)-12-oxo-9-octadecenoate gives rise to optically inactive methyl cis-8-[2-(2-oxooctyl)-cyclopropyl]octanoate.     

Sulfur ylides 13. Synthesis and intramolecular cyclization of keto-stabilized sulfur ylides

Keto-stabilized sulfur mono-and bisylides were obtained from N-phthalylglutamic acid and their intramolecular cyclization was studied. The intramolecular cyclization of the ylide obtained at the α-carboxy group gave a product of the pyrrolizidinedione structure; bisylide yielded a cycloheptene derivative as the result of intramolecular recombination of intermediate dicarbene. The ylide obtained at the γ-carboxy group underwent no cyclization, giving methylthio ketone and oxo benzoate. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2771–2776, December, 2005.     

Choice of polymer-bitumen binders for cast asphalt concrete mixes

Modification of bitumen with Kraton D1101 and D1192, Luprene LG 411 and 501, and DST-30-01 polymeric additives and the effect of these additives on the properties of cast asphalt concrete mixes were studied.     

Interaction of diazoalkanes with unsaturated compounds

The stereochemistry of cyclopropanation of norbornenes with diazomethane in the presence of Cu, Pd, and Rh compounds has been studied. Stereoselectivity of the cyclopropanation depends on the nature of the transition metal and does not depend on its valent state or ligand environment. The reaction proceeds predominantly asexo-cycloaddition of the methylene fragment. The greatest amount ofendo-isomer (up to 47 %) is formed in cyclopropanation of norbornadiene andexo-tricyclo[3.2.1.0^2,4]oct-6-ene in the presence of Cu and Rh compounds.For part 11 see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 733–735, April, 1993.     

Sulfur ylides 15. Intramolecular cyclization of new keto-stabilized sulfur bis-ylide

New sulfur bis-ylide was obtained from 3-amino-3-phenylpropionic acid and pyromellitic dianhydride. Its intramolecular cyclization proceeds regioselectively, leading to 3,4,11,12-tetrahydro-2H,6H-indolizino[2,1-f]pyrido[2,1-a]isoindole derivative in 66% yield. Phosphorus bis-ylide of similar structure gives a cyclization product in 10% yield. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2394–2396, December, 2007.     

Asphalt adsorption in relation to the surface area of the mineral filler and content of aromatic oils

The composition and properties of asphalts were examined in relation to the time of keeping at 160°C of asphalt-granite and asphalt-gabbro-diorite blends. The time of filling of the filler surface with the adsorbed asphalt components was established. A criterion was suggested for estimating the properties of asphalt during preparation and pouring of asphalt concrete.     

Influence of finely dispersed granite dust on the composition and properties of asphalt

Changes in the composition and properties of asphalt upon contact at 160°C with granite dust whose concentration in a mixture with asphalt was 40, 60, 70, and 85 wt % were examined.