I. V. Oleinik

Design of schiff base-like postmetallocene catalytic systems for polymerization of olefins: IV. Synthesis of 2-(aryliminomethyl)-pyrrole and 7-(aryliminomethyl)indole derivatives containing cycloalkyl substituents

Reactions of 4,6-substituted 2-cycloalkylanilines with 1H-pyrrole-2-carbaldehyde and 1H-indole-7-carbaldehyde in methanol in the presence of formic acid gave the corresponding Schiff bases which can be used as ligands for titanium and zirconium complexes.

Design of schiff base-like postmetallocene catalytic systems for polymerization of olefins: VIII. Synthesis of N-(o-cycloalkylphenyl) 2-hydroxynaphthalene-1-carbaldehyde imines

Substituted o-cycloalkylanilines reacted with 2-hydroxynaphthalene-1-carbaldehyde in methanol in the presence of formic acid to give the corresponding Schiff bases as ligands for the synthesis of titanium(IV) complexes.

Design of postmetallocene catalytic systems of aryliminetype for olefins polymerization: XIII. Synthesis of tetradentate bis(2-hydroxy-1-naphthaldimine) ligands and their complexes with titanium(IV) dichloride

Reactions of 2-hydroxy-1-naphthaldehyde with 1,4-diaminobutane, 1,6-diaminohexane, 4,4′-methylenedianiline and its alkyl- and cycloalkyl-sybstituted derivatives, with 4,4′-sulfonyldianiline, 2,2′- and 4,4′-oxydianiline, 4,4′-(1,4-phenylenebisoxy)dianiline, 4,4′-[propane-2,2-diylbis(1,4-phenylenebisoxy)]dianiline, and p-terphenyl-4,4″-diamine afforded a series of the corresponding diimines that at treating with TiCl2(OPr-i)2 formed mono- and binuclear complexes of titanium(IV) dichloride with tetradentate ligands LTiCl2 and L2(TiCl2)2.

Design of Schiff base-like postmetallocene catalytic systems for polymerization of olefins: IX. Synthesis of salicylaldehydes containing an isobornyl substituent and hydroxyphenyl imine ligands based thereon

Reactions of substituted 2-(1,7,7-trimethylbicyclo[2.2.1]hept-exo-2-yl)phenols with paraformaldehyde in the presence of tin(IV) chloride and 2,6-dimethylpyridine gave the corresponding salicylaldehydes which reacted with primary amines to produce a series of new Schiff bases as ligands for complex formation with transition metals.

Design of postmetallocene Schiff base-like catalytic systems for polymerization of olefins: XII. Synthesis of tetradentate bis-salicylaldehyde imine ligands

Reactions of salicylaldehyde, 3-tert-butylsalicylaldehyde, and 3,5-di-tert-butylsalicylaldehyde with 1,4-diaminobutane, 1,6-diaminohexane, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′,5,5′-tetramethyldiphenylmethane, 4,4′-diamino-5,5′-dicyclopentyl-3,3′-dimethyldiphenylmethane, 4,4′-diamino-5,5′-dicyclohexyl-3,3′-dimethyldiphenylmethane, bis(4-aminophenyl) sulfone, o,o′- and p,p′-diaminodiphenyl ethers, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 4,4″-diamino-p-terphenyl gave a series of the corresponding Schiff bases which can be used as tetradentate ligands for the synthesis of titanium and zirconium complexes.

Design of Schiff base-like postmetallocene catalytic systems for polymerization of olefins: V. Synthesis of salicylaldehyde imine ligands containing cycloalkyl substituents

Reactions of substituted cycloalkylanilines with salicylaldehyde, 3-tert-butylsalicylaldehyde, and 3,5-di-tert-butylsalicylaldehyde in methanol in the presence of formic acid gave a series of the corresponding Schiff bases as ligands for titanium(IV) complexes.

Design of Schiff base-like postmetallocene catalytic systems for polymerization of olefins: X. Synthesis of phenoxy imino ligands with bulky substituents

Reactions of primary amines with salicylaldehydes containing bulky substituents (tert-butyl, 2-phenylpropan-2-yl, triphenylmethyl) in positions 3 and 5 gave a number of new Schiff bases as ligands for complex formation with transition metals.

Convenient synthesis of 3,5-disubstituted N -Salicylidene-4-allyloxyanilines

Development of rational synthetic approaches to N-aryl salicylaldehyde imines having an allyloxy group in the imine fragment attracts interest since the use of such Schiff bases as ligands for phenoxy–imine complexes of titanium(IV) chloride ensures formation of effective self-immobilizing catalysts in the polymerization of ethylene and hence high molecular weight and good morphological parameters of the resulting polymer [1, 2]. Schiff bases I were previously [1] synthesized according to Scheme 1 via N-acetylation of p-aminophenol, O-allylation, removal of the acetyl protection, and condensation of p-allyloxyaniline thus obtained with substituted salicylaldehydes. We now propose a more convenient alternative procedure for the synthesis of Schiff bases I from p-aminophenol in a smaller number of steps. The procedure makes use of salicylidene protection of the amino group and includes reaction of 3,5-disubstituted salicylaldehydes IIa and IIb with p-aminophenol, followed by selective O-allylation of Schiff bases IIIa and IIIb at the hydroxy group in the imine fragment. Taking into account that allyl halide can be replaced by its homologs, the proposed scheme may be regarded as a rational general procedure for the preparation of ligands with variable length of alkenyloxy group. Salicylaldehyde imines IIIa and IIIb were synthesized in 95–96% yield by reaction of salicylaldehydes IIa and IIb with p-aminophenol in boiling methanol in the presence of a catalytic amount of formic acid. By heating Schiff bases IIIa and IIIb with allyl bromide in acetone in the presence of anhydrous potassium carbonate we obtained allyloxy derivatives Ia and Ib as the only products which were isolated in 98% yield