Electronic structure of aryl- and carbonyl-containing diazomethane derivatives,as disclosed by photoelectron spectroscopy

Vertical ionization energies (IE) of aryl and carbonyl derivatives of diazomethane have been determined by photoelectron spectroscopy. The types of the highest occupied molecular orbitals (HOMO) in these molecules are identified.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 325–328, February, 1993.     

Unusual isomerization of exo-exo-tetracyclo-[3.3.1.02,4.06,8]nonane

Conclusions exo-exo-Tetracyclo[3.3.1.0^2,4.0^6.8]nonane isomeirzes upon the action of catalytic amounts of boron trifluoride etherate or upon heating to exo-tricyclo[3.3.1.0^2,4]non-6-ene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 474–475, February, 1985.     

Reaction of diazoalkanes with unsaturated compounds. 11. Relative reactivity of olefins on catalytic cyclopropanation with diazomethane and palladium catalysts

The relative reactivity of unsaturated compounds on catalytic cyclopropanation with diazomethane in the presence of catalysts based on Pd²⁺ [Pd(OAc)₂, Pd(acac)₂, (PPh₃)₂·PdCl₂] has been studied using competing reactions. An interconnection was shown between the relative reactivity of the olefins and the coordinating activity of the C=C bond depending on its strain and spatial environment.For previous communication, see [1].Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences, 450054 Ufa; N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2353–2361, October, 1992.     

Reactions of diazoalkanes with unsaturated compounds 16. Catalytic reactions of diazomethane with 2-alkenyl-1,3-oxazolidines and 2-alkenyl-1,3-oxathiolanes

The influence of 1,3-oxazolidine and 1,3-oxathiolane fragments in substituted alkenes on the direction of their catalytic reaction with diazomethane has been investigated. The olefins bearing an oxazolidine substituent in the α- or γ-position and an oxathiolane substituent in the γ-position relative to the C=C bond react with diazomethane in the presence of Pd(acac)₂ selectively resulting in cyclopropanation products. The use of Cu(OTf)₂ does not result in cyclopropanation; however Cu(OTf)₂ catalyzes the reaction of diazomethane with 2-(alk-1-enyl)-1,3-oxathiolanes yielding 2,3,5,6-tetrahydro-1,4-oxathiocines formed through the [2,3]-sigmatropic rearrangement of the intermediate sulfonium ylides. For Part 15 see Ref. 1. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 604–608, March, 2008.     

Effect of sodium-carboxymethylcellulose on inhibition of scaling by calcium carbonate and sulfate

Sodium-carboxymethylcellulose inhibits the crystallization of calcium carbonate and sulfate on the surface of stainless steel in a supersaturated aqueous solution at 80°C. An increase in the size of calcium carbonate crystals and a change of their structure is observed in the presence of sodium-carboxymethylcellulose. The data obtained indicate that development of new “green” reagents for oil and gas extraction, scale inhibitors, on the basis of sodium-carboxymethylcellulose is promising.     

Cu(OAc)2-2,4-lutidine-ZnCl2 as an effective catalyst of functionalization of isobutylene oligomers and 1,2-polybutadiene with methyl diazoacetate

The possibility of [1+2]-cycloaddition of methoxycarbonylcarbene generated by catalytic decomposition of methyl diazoacetate in the presence of the Cu(OAc)₂-2,4-lutidine-ZnCl₂ system to the carbon-carbon double bound in isobutylene oligomers and syndiotactic 1,2-polybutadiene was examined. A comparative analysis of physicochemical properties of the starting compounds and their functionalized products was performed.     

Synthesis of <Emphasis Type="Italic">N</Emphasis>-(2-aminoethyl)- and <Emphasis Type="Italic">N</Emphasis>-(3-aminopropyl)cytisine

2-(N-cytisinyl)acetamide or 3-(N-cytisinyl)propanamide were prepared by treatment of the methyl esters of N-cytisinylacetic or 3-(N-cytisinyl)propanoic acids with aqueous NH₄OH. N-(2-Aminoethyl)-or N-(3-aminopropyl)cytisine was synthesized by reduction of the amide with (i-Bu)₂AlH.     

Phosphazenes: I. Reactions with electron-deficient alkenes

Triphenylphosphazenes reacted with methyl vinyl ketone, methyl acrylate, methyl methacrylate, and dimethyl maleate to give the corresponding substituted dihydropyrazoles.     

Reactions of diazoalkanes with unsaturated compounds 15. Catalytic reactions of unsaturated carbonyl compounds and their derivatives with diazomethane

The present study concerned with the influence of the nature of the acetal fragment in unsaturated compounds on the reactivity of the C=C bond in cyclopropanation reactions with diazomethane catalyzed by copper and palladium compounds. The acetal substituents at the α- or γ-position with respect to the C=C bond were found to exert an activating effect on the yields of cyclopropanation products compared to the starting unsaturated carbonyl compounds, which give 1,3-dipolar cycloaddition adducts with CH₂N₂ as by-products. Cyclopropanation of the double bonds appeared to be most efficiently catalyzed by Pd(acac)₂. Dedicated to Corresponding Member of the Russian Academy of Sciences E. P. Serebryakov on the occasion of his 70th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 979–983, April, 2005.