T. Klimova

The reactions of semicarbazide and thiosemicarbazide with ferrocenyl-substituted α,β-enones

Abstract Semicarbazide (hydrochloride) and thiosemicarbazide react with α,β-unsaturated ketones of the ferrocene series in excess of t BuOK to give 1-carbamoyl- and 1-thiocarbamoyl(ferrocenyl)-4,5-dihydropyrazoles. The condensation with thiosemicarbazide is accompanied by the fragmentation of the starting α,β-enones resulting in ferrocenecarbaldehyde or acetylferrocene thiosemicarbazones.

Stereoselectivity of formation of polycyclic ferrocenyl-4,5-dihydropyrazoles based on E- and Z-s-cis-α,β-enones

Abstract Reaction of E- and Z-isomeric 2-ferrocenylmethylidene-1-tetralone, 2-ferrocenylmethylidene-3-quinuclidinone, 1-methyl-3-ferrocenylmethylidene-4-piperidone and 2-ferrocenylmethylidenetropinone with hydrazine proceeds stereospecifically with the formation of the same diastereomeric polycyclic ferrocenyldihydropyrazoles independently of the geometric configuration of the starting α,β-unsaturated ketones. X-ray structural analysis is presented for the trans-diastereomer of 4-acetyl-3-ferrocenyl-1,4,5-triazatricyclo[5.2.2.02,6]undec-5-ene.

Synthesis of cyclotriveratrylene dendrimers and their supramolecular complexes with fullerene C60

Dendrimers with cyclotriveratrylene core and polybenzyl ether branches were synthetised by a convergent Fréchet approach. The cyclotriveratrylene was obtained by trimerisation of phenolic allyl ether of vanillyl alcohol and its structure was characterised by X-ray diffraction. The synthesised dendrimers of first and second generations were used to obtain the supramolecular complexes with fullerene C60. The ability of the fullerene C60 to form supramolecular complexes with the cyclotriveratrylene dendrimers was confirmed by 1H and 13C NMR studies. The value of the association constant K a = 678 ± 60 mol− 1 dm3 calculated on the basis of UV–vis spectroscopic measurements for the titration of the fullerene C60 solution in toluene with increasing amount of the cyclotriveratrylene dendrimer suggest that the fullerene resides mainly near the central core. All the compounds were characterised by 1H, 13C NMR, FTIR, UV–vis spectroscopy, MALDI-TOF, FAB+ mass spectra and elemental analysis.

Synthesis of Tetrabenzoxazines and Their Supramolecular Complexes with Fullerene C60

Abstract The extension of the deep cavity of resorcinarenes by the regioselective Mannich reaction is reported. X‐ray studies showed that all the tetrabenzoxazines were obtained as one regioisomer, as well as a single epimer in the case of chiral amines. In order to elucidate the ability of the synthetized tetrabenzoxazines to host large molecules, two new supramolecular complexes with fullerene C60 were obtained and characterized. Both types of resorcinarenes, chiral and nonchiral, were tested. The formation of tetrabenzooxazine:C60 1:1 supramolecular complexes was observed and confirmed by elemental analysis and 13C CP‐MAS NMR spectroscopy.

Synthesis of Dendrimers with Porphyrine Core and their Supramolecular Complexes with Fullerene C60

Dendritic branches of poly(arylether) with peripheral butyl chains have been attached to a porphyrine core. Dendrimers of first, second and third generation were synthesized. Viability to form supramolecular complexes with fullerene C60 was studied with two dendrimers of second and third generation. The supramolecular complexes were characterized by 1H, 13C NMR in solution, FTIR, UV-vis spectroscopy and elemental analysis.

Supramolecular Complexes of Resorcinarene‐Dendrimers and Fullerene C60

Abstract Dendritic branches of poly(arylether) with peripherial n‐propyl chains have been attached to a resorcinarene core. Viability to form supramolecular complexes with fullerene C60 was studied with dendrimers of first and second generation. All the compounds were characterized by 1H, 13C NMR, FTIR, UV‐vis spectroscopy, MALDI‐TOF, FAB+ mass spectra and elemental analysis.

2,3-Diferrocenylcyclopropenone in the reaction with organomagnesium compounds

The reactions of 2,3-diferrocenylcyclopropenone with ethyl- and benzylmagnesium chlorides afford 3,3-diethyl- and 3,3-dibenzyl-1,2-diferrocenylcyclopropenes along with products of nucleophilic opening of the three-membered ring: α,β-unsaturated and saturated ketones (cis-1,2-diferrocenylpent-1-en-3-one and cis-1,2-diferrocenyl-4-phenylbut-1-en-3-one, 4,5-diferrocenylheptan-3-one, and 3,4-diferrocenyl-1,5-diphenylpentan-2-one). The products of insertion of intermediate diferrocenyl(vinyl)carbene at one of the σ-bonds of the starting 2,3-diferrocenylcyclopropenone were also isolated: 4-(2-oxo-1-ferrocenylbutyl)- and 4-(2-oxo-3-phenyl-1-ferrocenylpropyl)-2,3,4-triferrocenylcyclobutenones. 3,3-Dibenzyl-1,2-diferrocenylcyclopropene and one of the diastereomers of 4,5-diferrocenylheptan-3-one were studied by X-ray diffraction analysis.

Synthesis of ferrocenyl-3,4-dihydro-1H-pyrimidin-2-ones

Methylurea reacts with linear and cyclic α,β-enones of the ferrocene series to yield ferrocenyl-3-methyl-3,4-dihydro-1H-pyrimidin-2-ones characterized by IR and 1 H and 1 3 C NMR spectroscopical data. The structure of 4-ferrocenyl-6-(4-methoxyphenyl)-3-methyl-3,4-dihydro-1H-pyrimidin-2-one is confirmed by X-Ray diffraction analysis.

3-Alkenyl-5-ferrocenyl-2-pyrazolines in reactions with azodicarboxylic acidN-phenylimide

Azodicarboxylic acidN-phenylimide reacts with 1-acetyl-3-(2-ferrocenylethenyl)-5-ferrocenyl-2-pyrazoline according to the [4+2]-cycloaddition mechanism to form a Diels—Alder adduct. Under analogous conditions, 1-acetyl-5-ferrocenyl-3-(1-cyclohexenyl)-substituted 2-pyrazolines containing allylic hydrogen atoms give monoene addition products.

Synthesis of Porphyrin Derivative with Four Fullerene C60 Moieties

In the present work, we report the synthesis of porphyrin derivative joined by Williamson reaction with fullerene C60-containing substituents. The structure of this compound was confirmed by 1H, and 13C NMR in solution, FTIR, UV-vis, MALDI-TOF spectroscopy and elemental analysis.