Search

The preparation of mono-, di- and trisubstituted gallic derivatives is described using either 1-bromododecane or 12-bromo-1-dodecanol. After saponification of the methyl ester bearing the dodecanol groups, subsequent functionalization with methacryloyl chloride provides the hybrid methacrylate esters/anhydride species. Selective cleavage of the anhydride function gives rise to the corresponding acids, which have been further functionalized to the imine derivative 15 by condensation with 4-[imino-4-(toluyl)]phenol. This reaction is made possible using the acidic form of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC·HCl) and dimethylaminopyridine (DMAP). Selective hydrolysis of the imine function with a HCl-treated silica provides the targeted aniline in excellent yield.

The preparation of 1,3-bis-(4-dodecyloxy-phenyl)-3H-imidazol-1-ium trifluoro-methanesulfonate is described from the 4-dodecyloxy phenylamine derivative. This new imidazolium salt exhibits a lamellar liquid crystal mesophase between 119 and 172 °C. The Smectic A phase has been characterised by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction. In addition the lamellar crystallographic structure obtained on single crystal is reported and corroborated the self-assembly of molecules in the mesomorphic state.

The anodic behaviour of the ferrocenyl-derived compounds [Ph 2 PCH 2 C(O)(η 5 -C 5 H 4 ) Fe(η-C 5 H 5 )] ( 1 ), [( o -C 6 H 4 CH 2 NMe 2 )PdPh 2 PCHC(O)(η 5 - C 5 H 4 )Fe(η 5 -C 5 H 5 )] ( 2 ) and [( o -C 6 H 4 CH 2 NMe 2 )Pd-ClPh 2 PCH 2 C(O)(η 5 -C 5 H 4 )Fe(η 5 -C 5 H 5 )] ( 3 ) has been investigated in dichloromethane at a platinum electrode. Voltammetric and coulometric data, and spectral results, indicate that for each compound, the first electron loss corresponding to the oxidation of the ferrocenyl centre triggers an intramolecular electron transfer. In complexes 2 and 3 , this results in the formation of transient radical cationic Pd III species whereas for 1 the electron transfer probably leads to a phosphonium cation radial.

The reaction of cis-[ Pd{Ph 2 PCHC(O )Ph}2] (1) with HBF4/H2O instantly leads to the formation of the cationic complex cis-[ Pd{Ph 2 PCH 2 C(O )Ph}2][BF4]2. When 1 was treated with commercial BF3·Et2O, containing HBF4 as an impurity, the related compound cis-[ Pd{Ph 2 PCH 2 C(O )Ph}2][BF4][B2F7] (2) was formed. The structure of 2 was determined by an X-ray diffraction study. The compound ctystallizes in the orthorhombic system, P212121 space group, Z=4, cell dimensions: a=16.474(4), b=19.007(5), c=12.932(4) A, V=4049.3 A3, final R=0.030. The two chelating phosphines define puckered five membered metallocycles characterised by PCH2 carbon atoms lying significantly out of the metal coordination plane (−0.617(7) A for C1 and +0.779(7) A for C21). This study establishes the first structural data for the B2F7− anion: the value of the BFbridgeB angle is 128.1(7)°. The values of the BFbridge bond lengths (1.50(1) and 1.51(1) A are significantly longer than the other BF bonds (1.34–1.39 A).