Reactions of diazoalkanes with unsaturated compounds

A systematic study has been conducted of the catalytic reaction of diazomethane with cyclic and polycyclic unsaturated hydrocarbons, conjugated dienes, as well as with a series of functionalized unsaturated compounds. The feasibility of using transition metal, nontransition metal, and rare earth metal compounds of, for example, Co, Ni, Zr, Cr, Rh, and Dy, has been demonstrated for the first time. It has also been established that Pd(acac)₂ has very high activity as a catalyst for the cyclopropanation of terminal and endocyclic double bonds by diazomethane, and that its activity is reduced upon the introduction of n-donor ligands or in the presence of strong polar solvents.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1861–1869, August, 1989.     

Reactions of highly electrophilic polyfluoro unsaturated compounds with pyrazole derivatives

Pyrazole derivatives were hydroxyalkylated at the C⁴ atom by hexafluoroacetate and methyl trifluoropyruvate. The products of the hydroxyalkylation were dehydrated to the corresponding alkylidene derivatives which were reacted with nucleophiles. Dicyanoethylenes, obtained from polyfluorocarbonyl compounds, alkylated pyrazol-5-ones with the formation of pyrazolopyran derivatives.A. N. Nesmeyanov Institute for Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2617–2623, November, 1992.     

Pyridazines. LXX. Reactions of azidoazolopyridazines with unsaturated compounds

Cycloaddition reactions of azidoazolopyridazines with unsaturated esters, cyclic enol ethers, styrene, 2-vinyl-pyridine, bicyclo[2.2.1]heptene, dicyclopentadiene and dehydrobenzene were investigated. The reaction proceed via the intermediate Δ² -1,2,3-triazolines which were in most cases termolabile and decomposed further to give the final products which were enamines, imines of fused aziridines.     

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.     

Reactions of diazo ketones with activated unsaturated compounds in the presence of gallium trichloride

Diazoacetone reacts with methyl acrylate in the presence of anhydrous GaCl₃ to give isomeric methyl 2-acetylcyclopropanecarboxylates rather than pyrazolines obtained from diazo esters or by noncatalytic reactions. In a similar reaction, diazoacetophenone yields methyl 2-benzoylcyclopropanecarboxylates, benzoylmethyl acrylate, and benzoylmethyl 2-benzoylcyclopropanecarboxylate via partial transesterification. Addition of an equimolar amount of GaCl₃ to diazoacetone in the system CH₂Cl₂-HCl-H₂O unexpectedly produces 4,5-dimethylfuran-3(2H)-one and 1,1′-oxybis(propan-2-one).     

Reactions of 9-chloro-1,10-anthraquinone 1-dichlorophosphorylimine with N- and C-nucleophiles

9-Chloro-1,10-anthraquinone 1-dichlorophosphorylimine formed in the reaction of 1-amino-9,10-anthraquinone with PCl₅ followed by dehydrochlorination reacts with primary amines with substitution of chlorine atoms. In the case of aliphatic amines, the reaction occurs further concurrently in two directions: the addition of the amine molecule with the formation of 9,9-di(alkylamino) derivatives of the anthrone and the substitution of hydrogen atom at position 4 with the formation of 4,9-di(alkylamino) derivatives of 1,10-anthraquinone 1-imine. In the case of aromatic amines, 1-amino-9,10-anthraquinone 9-arylimines are the end products. Reactions with the anions of CH-acids containing an alkoxycarbonyl or cyano group occur with substitution in position 9 followed by intramolecular cyclization with the formation of 2-alkoxy- or 2-amino-7H-dibenzo[f,ij]isoquinolin-7-one derivatives, respectively. For preliminary communication, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1179–1184, June, 1998.     

C-Nitroso compounds—XXXV : Reaction of organometallic compounds with 1-chloro-1-nitroso-2,2,6,6-tetramethylcyclohexane

Reaction of Grignard reagents and organolithium compounds (RM) with the congested 1-chloro-1-nitroso-2,2,6,6-tetramethylcyclohexane 1 leads to the formation of significant amounts of the reduction product 2,2,6,6-tetramethylcyclohexanone oxime 3 (61–90%) together with the corresponding oxime O-R ether 4 (0–11%). Attack on nitrogen is unimportant as shown by very low yields of nitrone. Formation of the products is rationalised with a pathway involving transfer of an electron from RM to 1. This leads—after separation of MCI—to a radical pair consisting of R and the relatively stable iminoxy radical 2 (Schemes 1 and 2). Combination of these radicals explains formation of oxime ether 4 and nitrone 5, while reaction of iminoxy radical 2 with excess of RM can give oxime 3. Reactive radicals R (i.e. Me, Ph, and to a minor extent n-Bu) are furthermore capable of abstracting hydrogen from the solvent (diethyl ether, toluene, or cumene), and the solvent derived radicals can also combine with 2 on oxygen, under formation of oxime ether (26% of 6a). The corresponding benzyl- and cumyl ethers 6b and 6c are only formed in trace amounts because dimerisation of benzyl radicals (7%) and cumyl radicals (22%) is favoured.     

Reactions of pyrimidinols and pyrimidinethiols with 2-chloroethanol and with 2-chloro-1-propanol

Conclusions In the reactions of pyrimidinethiols and pyrimidinols with 2-chloroethanol and 2-chloro-1-propanol 2-(pyrimidinylthio)alkanols and N-(hydroxyalkyl)pyrimidinones are formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1613–1617, September.     

Reactions of α-chloronitrones with unsaturated ethers

The Ag⁺ induced reaction of α-chloronitrones with unsaturated ethers goes in two parallel competitive directions. On the one hand cycloadducts like 3 are formed and on the other hand oxonium ions like 4. Formation of analogous oxonium compounds occurs also when α-alkoxynitrones are treated with Et₃O⁺BF₄^? in 1,2-dichloroethane. Formation of oxonium compounds with the enol-ethers is practically irreversible and leads to enol-ether fragmentation. With the saturated ethers compounds like 25 were formed and were used as a potential source of N-alkyl-N-vinyl-nitrosonium ions.     

Reactions on polymers with amine groups. I. Reactions of vinylpridine polymers and of their model compounds with unsaturated carboxylic acids

The reactions of vinylpyridine polymers with α,β-unsaturated carboxylic acids such as acrylic, methacrylic, crotonic, itaconic, cinnamic, fumaric, and maleic acids were studied. It was found that, when reacted with acrylic, itaconic and fumaric acids. poly(4-vinylpyridine) gave macromolecular betaine products while with maleic acid, betaine as well as the corresponding salt was obtained. Poly(2-vinylpyridine) reacted with the same acids as poly(4-vinylpyridine) gave only the salts. No significant changes were observed with the two polymers when reacted with methacrylic, crotonic, and cinnamic acids. To attempt to rationalize these observations with the two macromolecular tertiary amines, the reactions of 4-methyl and 2-methylpyridines with the same carboxylic acids were investigated. The ¹H-NMR methodology was generally applied to elucidate the chemical structure obtained. © 1995 John Wiley & Sons, Inc.