Reaction of diazoalkanes with unsaturated compounds Communication 1. Cyclopropanation of olefins with diazomethane in the presence of copper compounds

Conclusions In the presence of CuCl or (PhO)3P·CuCl diazomethane cyclopropanates cycloalkenes and cyclodienes with various different structures. When this is done the yields of the cyclopropane compounds increase as the size of the ring and its degree of conjugation increases. This is in accord with the change in the stability of the copper complexes of these olefins which are formed under the reaction conditions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 119–124, January, 1984.Results partially presented at the Twelfth Mendeleev Congress on General and Applied Chemistry in Baku [1].     

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.     

Reaction of diazoalkanes with unsaturated compounds

A THF solution of diazopropyne was obtained in 60% yield by the reaction of a 30% aqueous solution of methylamine withN,N′-dinitroso-N,N′-dipropargylterephthalodiamide. The reactions of diazopropyne with methyl acrylate and methyl methacrylate giving various ethynylpyrazolines as well as its CuCl-catalyzed decomposition in the presence of norbornene or norbornadiene yielding ethynylcyclopropanes were studied. The main products of catalytic deazotization of diazopropyne in the absence of unsaturated compounds are isomericE- andZ-hex-3-ene-1,5-diynes resulting from propargylene dimerization. For Part 12, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2278–2282, November, 1998.     

Reaction of α-Haloketones with ortho-Dihydroxy-2H-1-benzopyran-2-ones. Formation of α-Pyrano-1,5-benzodioxapines-A New Heterocyclic System

Reaction of 7,8-dihydroxy-2H-1-benzopyran-2-one, and its 4-methyl derivative, with α-haloketones affords α-pyrano-1,5-benzodioxapines, while 3-chloro-4-methyl-7,8-dihydroxy-2H-1-benzopyran-2-one gives α-pyrano-1,4-benzodioxane. The structures of the compounds were deduced using a combination of ¹H nmr, ¹³C nmr (BB, DEPT), HETCOR, NOESY, and selective INEPT techniques and molecular modeling.     

Reaction of unsaturated compounds with diazoalkanes. Communication 3. Cyclopropanation of cyclooctatetraene with diazomethane

Conclusions The cyclopropanation of the double bonds in cyclooctatetraene by diazomethane in the presence of cuprous chloride is nonregioselective and leads to the formation of the corresponding mono-, di-, tri-, and tetracyclopropanation products with yields determined by the amount of added diazomethane. The obtained bis-, tris-, and tetrakishomocyclooctatetraenes are characterized by a preference for the isomers with the exo orientation of the cyclopropane fragments.For Communication 2, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 77–84, January, 1986.     

Reaction of NO2BF4, with olefins in acetic anhydride. 1. Nitration of cyclenes

Conclusions The conjugated nitration of cyclic olefins by NO₂BF₄ in acetic anhydride, whose course is greatly dependent on the structural features of the olefins undergoing nitration has been studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2286–2292, October, 1977.     

Reaction of diazoalkanes with unsaturated compounds. 9 Catalyzed cyclomethylenation of trimethylsilylacetylenes by diazomethane

The catalyzed reaction of methyl-, propyl-, and cyclopropyltrimethylsilylacetylenes with diazomethane in the presence of CuCl leads to the corresponding cyclopropenes and bicyclobutanes with overall yields of up to 70%, and also to the products of incorporation of a methylene group into the C³-H bond of the cyclopropenes formed (2–9%). Partial catalyzed isomerization of the 1-trimethylsilyl-2-cyclopropylcyclopropene formed from trimethylsilylcyclopropylacetylene, into 1-trimethylsilyl-1-cyclopropylallene (yield 50%) was discovered to proceed under the reaction conditions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1141–1146, May, 1990.     

Reaction of 2,3-dihydro-4-phenyl-1H-1,5-benzodiazepinethione-2 with acetylhydrazine

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, p. 1430, October, 1991.     

Reaction of carbonyl compounds with diazoalkanes as a method for epoxide synthesis. A review

The application of the reaction of carbonyl compounds with diazoalkanes the preparation of epoxides is reviewed. The effects of the structures of the reagent and substrate and of the solvent on the reaction course and product yield are examined. The stereochemistry of epoxide formation is discussed.Belorus State Technological University, 220630 Minsk. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 291–309, March, 1995. Original article submitted July 29, 1994.     

2-Carbethoxymethyl-4H-3,1-benzoxazin-4-one. 4. Reaction with anilines

In a solution of DMF, 2-carbethoxymethyl-4H-3,1-benzoxazin-4-one reacts with primarily aromatic amines basically with the formation of the corresponding 2-carbethoxymetlzyl-3-arylquinazolin-4(3H)-ones. Possible mechanisms of these chemical transformations are reported and discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 225–228, February, 1994. Original article submitted June 28, 1993.