A new approach to ferrocene derived alkenes via copper-catalyzed olefination.

A new approach to ferrocenyl haloalkenes and bis-alkenes was elaborated. The key procedure involves copper catalyzed olefination of N-unsubstituted hydrazones, obtained from ferrocene-containing carbonyl compounds and hydrazine, with polyhaloalkanes. The procedure is simple, cheap and could be applied for the utilization of environmentally harmful polyhalocarbons. The cyclic voltammetry study of the representative examples of the synthesized ferrocenyl alkenes shows the strong dependence of the cathodic behavior on the amount of vinyl groups: while for the monoalkene containing molecules no reduction is seen, the divinyl products are reduced in several steps.

Experimental and Theoretical Study of an Intramolecular CF3-Group Shift in the Reactions of α-Bromoenones with 1,2-Diamines.

The reactions of trifluoromethylated 2-bromoenones and N,N'-dialkyl-1,2-diamines have been studied. Depending on the structures of the starting compounds, the formation of 2-trifluoroacetylpiperazine or 3-trifluoromethylpiperazine-2-ones was observed. The mechanism of the reaction is discussed in terms of multistep processes involving sequential substitution of bromine in the starting α-bromoenones and intramolecular cyclization of the captodative aminoenones as key intermediates to form the target heterocycles. The results of theoretical calculations are in perfect agreement with the experimental data. The unique role of the trifluoromethyl group in this reaction is demonstrated.

Design and synthesis of a new family of fluorinated liquid crystals.

A convenient and simple three-step pathway to the new family of CF(2)CF(2)S-bridged alkanes and CF(2)S-, CF(2)O-bridged alkenes and alkynes was elaborated by using catalytic olefination reaction as a key step of the synthetic sequence. The obtained compounds revealed attractive liquid crystalline characteristics.

[N-(1-Aza-nidyl-2,2,2-trichloro-ethyl-idene)-2,2,2-trichloro-ethanimidamide]-copper(II).

The title compound, [Cu(C(4)H(2)Cl(6)N(3))(2)], was obtained by the reaction of CCl(3)CN with ammonia in presence of CuCl. The Cu(II) atom is located about an inversion centre. The mol-ecule consists of three planar units (one central square CuN(4) and two C(2)N(3) fragments), adopting a staircase-like structure. The six-membered metallocycles have a sofa conformation with the Cu atom out of the plane of the 1,3,5-triaza-penta-dienyl ligands by 0.246 (5) Å. The ipso-C atoms of the CCl(3) substituents are slightly out of the 1,3,5-triaza-penta-dienyl planes by 0.149 (6) and -0.106 (6) Å. The CCl(3) groups of each 1,3,5-triaza-penta-dienyl ligand are practically in the energetic-ally favourable mutually eclipsed conformation. In the crystal, the mol-ecules are packed in stacks along the a axis. The mol-ecules in the stacks are held together by two additional axial Cu⋯Cl inter-actions of 3.354 (2) Å. Taking the axial Cu⋯Cl inter-actions into account, the Cu(II) atom exhibits a distorted [4 + 2]-octa-hedral coordination environment. The stacks are bound to each other by weak inter-molecular attractive Cl⋯Cl [3.505 (2)-3.592 (3) Å] inter-actions.