Synthesis and carbene decomposition of functionally substituted diazoacetate esters. 6. Propargyl diazoacetate

A synthesis of propargyl diazoacetate (I) was carried out and its chemical transformations were studied. The reaction of (I) in the presence of Rh(OAc)₂ at 25C with 1-pentyne gives the propargyl ester of l-propylcyclopropene-3-carboxylic acid in 80% yield, while reaction with 2,3-dimethyl-2-butene at 60C results in the propargyl ester of tetramethylcyclopropanecarboxylic acid in 10% yield. Compound (I) reacts under the same conditions (35–60C) with ether, CH₂Cl₂ and water, with the formation of propargyl esters of ethoxyacetic, 2,3-dichloropropionic, and a mixture of glycols and 2-[(propyn-2-yl)-oxycarbonyl]methoxy acetic acids in yields of up to 35%. A spontaneous oligomerization of (I) was observed as a result of a dipolar [1, 3]-cycloaddition of the CH=N₂ fragment of one molecule of (I) to the terminal triple bond of the second molecule with the formation of oligomers of 3-hydroxymethylpyrazole-5-carboxylic acid.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1051–1056, May, 1991.     

C-hydroxyalkylation of N-adamantylanilines by hexafluoroacetone and methyl trifluoropyruvate

N-(1-Adamantyl)-4-(1-hydroxy-1-trifluoromethyl- 2,2,2- trifluoroethyl)aniline (III) and N-(1-adamantyl)-4-(1-hydroxy-1-methoxycarbony 1-2,2,2-trif luoroethyl) aniline (IV) were obtained by the reaction of N-(1-adamantyl)aniline with ketone (I) and ketoester (II). Analogous procedures gave N-(2-adamantyl)- 4- (1-hydroxy- 1-trifluoromethyl- 2, 2,2-trifluoroethyl)aniline (V) and N-(2-adamantyl)-4-(1-hydroxy-1-methoxycarbonyl-2,2,2-trifluoroethyl)aniline (VI). The action of hydrogen peroxide on (III) in the presence of sodium tungstenate gave N- (1- adamantyl)- 4- (1- hydroxy- 1- trifluoromethyl- 2,2,2- trifluoroethyl)aniline N-oxide (VII).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2348–2350, October, 1989.     

New examples of the vinylation of NH-heterocycles with acetylene at atmospheric pressure in the KOH-DMSO system

Vinylation of 2-hetarylpyrroles, 4,5-dihydrobenzo[g]indole, and 1,2,3,4-tetrahydro--carbinols at atmospheric pressure in the superbasic system KOH-DMSO at 100–120 ° C has given the corresponding N-vinyl derivatives in yields of 92–99%.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 481–485, April, 1986.     

Synthesis of benzyl esters of 2,2-dimethyl-3-(4-difluoromethoxyphenyl)-cyclopropane carboxylic acid — cyclic analogs of pyrethroid fluorocitrinate

3-Phenoxybenzyl and -cyano-3-phenoxybenzyl esters of 2,2-dimethyl-3-(4-difluoromethoxyphenyl)cyclopropane carboxylic acid have been synthesized. The latter compound, which is the cyclopropane analog of pyrethroid fluorocitrinate, has moderate insecticide activity toward the housefly.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 652–656, March, 1990.     

Rearrangement of the benzyl benzoate molecular ion to lose H2O

The molecular ion of benzyl benzoate undergoes several decompositions, two of which are the loss of H 2 O and COOH·. To study these processes, the mass and IKE spectra of benzyl benzoate together with various deuterated benzyl benzoates and some of its isomers were studied. Evidence is presented to support the rearrangement processes of the molecular ion. A decomposition scheme is proposed to explain the observed transitions.