M. A. Galkina

Synthesis of bis(2-cyanoacrylates) from 2-cyanoacryloyl chloride and 2-butene- and 2-butyne-1,4-diols

The interaction of 2-cyanoacryloyl chloride with unsaturated 1,4-diols leads to bis(2-cyanoacrylates) with a double or triple C-C bond.

Intramolecular electrophilic rearrangements in saturated acyclic systems. Reactivity of the zwitterion derived from triisopropylphosphine and ethyl 2-cyanoacrylate with respect to different types of electrophiles

The reactions of the zwitterion derived from triisopropylphosphine and ethyl 2-cyanoacrylate with mercuric chloride and aryl isothiocyanates containing Cl atoms in the ortho positions of the benzene ring follow an unusual pathway because this zwitterion represents “latent” triisopropylphosphine due to the reversibility of the reaction of triisopropylphosphine with ethyl 2-cyanoacrylate. The molecular structures of the adducts of triisopropylphosphine with 2,6-dichloro- and 2,4,6-trichlorophenyl isothiocyanates were confirmed by X-ray diffraction study. Protonation of the adduct of triisopropylphosphine with 2,6-dichlorophenyl isothiocyanate occurred at the nitrogen atom, whereas methylation with methyl trifluoromethanesulfonate afforded an S-methylation product. The results of X-ray diffraction study of the resulting compounds are presented.

Reactions of distabilized β-dicarbonyl sulfonium and iodonium ylides with isocyanates

The reactions of tosyl isocyanate with diethyl diphenylsulfuranylidenemalonate, 2-dimethylsulfuranylidenedimedone, and 2-dimethylsulfuranylideneindane-1,3-dione afforded 1,3-ditosyl-5,5-diethoxycarbonylimidazolidine-2,4-dione and tosylimination products at the keto groups, respectively. Phenyliodonium ylides derived from diethyl malonate and ethyl acetate react with 3,4-dichlorophenyl isocyanate to form substituted oxazolin-2-ones.

Electrophilic 1,3-C→N− and-N→C− migrations in saturated systems

A new type of intramolecular electrophilic rearrangements involving the shift of COOAlk groups from carbon to an N-anionic center is considered. Carbanionic species with COOAlk groups at anionic centers containing no acidic hydrogen react unusually with alkyl(aryl) iso(thio)cyanates giving carbamates as a result of insertion of RNCX into the C−C bond. The kinetics and mechanism of insertion of aryl isocyanates into the C−C bond of the phosphonium zwitterion obtained from triisopropylphosphine and ethyl 2-cyanoacrylate are discussed. The reaction of α-carbanions derived fromN,N-disubstituted amides with methyl trifluoromethanesulfonate results inO-methylation. Some possibilities of back N→C− migrations are considered.

Synthesis and X-ray Structural Study of 1-adamantylmethyl 2-cyanoacrylate and 1,10-decanediol bis-2-cyanoacrylate

I-Adamantylmethyl 2-cyanoacrylate (1) was prepared by the reaction of 2-cyanoacryloyl chloride with 1-adamantylmethanol . 1,10-Decanediol bis-2-cyanoacrylate (2) was synthesized by transesterification of methyl 2-cyanoacrylate with 1,10-decanediol. Esters1 and2 were studied by X-ray structural analysis.

Addition of thiols and thioacids to ethyl-α-cyanoacrylate

Various sulfhydryl compounds RSH (R=alkyl, aryl, acetyl, diethoxyphosphoryl and diethoxythiophosphoryl), unlike their oxygen analogs, easilyattack ethyl-α-cyanoacrylate forming adducts RSCH2CH(CN)COOC2H5 with high yields.

Reactions of isocyanates with compounds containing active methylene groups in the presence of triethylamine

Compounds containing active methylene groups react with isocyanates of different structures in the presence of triethylamine to form functionally substituted amides.

Salts of α-cyanoacrylic acid with sterically hindered tertiary amines

Syntheses are reported for representatives of a new class of derivatives of α-cyanoacrylic acid, namely, its salts with brucine, tert-butyldimethylamine, and diisopropylmethylamine.

Reaction of α-cyanoacrylic acid catalyzed by tertiary amines

The action of pyridine on a-cyanoacrylic add leads to the rapid and quantitative formation of 2,4-dicyano-4-pentenoic add. In the presence of excess p-nitro-benzaldehyde, 1-hydroxy-1-p-nitrophenyl-2-cyano-2-butene is formed in this reaction in addition to 2,4-dicyano-4-pentenoic add.

Aza-Michael reaction as an efficient method for the synthesis of first representatives of β-azahetaryl-β-diphenylphosphorylalkanones

Aza-Michael reaction of (E)-4-(diphenylphosphoryl)but-3-en-2-one (1) with a number of mono-and bicyclic nitrogen heterocycles proceeds regioselectively in the absence of catalysts with the formation of corresponding β-azahetaryl β-diphenylphosphoryl ketones; in the case of imidazole, the presence of chiral organic catalysts allows one to increase the yields of the adducts and to obtain them in enantiomerically enriched form.