Enantioselective Synthesis Of 1,1'-Binaphthalene-2,2'-diol And Study On Magnetic Properties Of Rare Earth Metal Complexes Containing TCNQ

Firstly, several chiral bibenzimidazole compounds and several chiral amino acidderivatives, (1R,2R)-bis(1-H-benzimdazol-2-yl)ethane-1,2-diol (BBImED),(1S),2-bis-(1-H-benzimidazol-2-yl)ethylamine (BBImEA),(1S),3-bis-(1-H-benzimdazol-2-yl)-1-propylamine (BBImPA), (L)-proline ethyl ester(PEE), (L)-phenylalanine ethyl ester (PAEE), (L)-phenylalanine iso-propyl esterhydrochloride (PAiPE·HCl), (L)-phenylalanine n-butyl ester (PAnBE), (L)-tyrosinemethyl ester (TME), (L)-tyrosine ethyl ester (TEE), and a new optically activecompound, (1S)-(1-H-benzimidazol-2-yl)-2-(p-hydroxyphenyl)ethylamine(BImpHPEA), are synthesizedby the reaction of(L)-tartaric acid,(L)-aspartic acid,(L)-glutamic acid, (L)-proline, (L)-phenylalanine, (L)-tyrosine as substrates withseveral low-molecular-weight aliphatic alcohols and o-phenylenediamino,respectively. These compounds are characterized by IR spectra, 1H NMR spectra,elementalanalysesandopticalactivity.Secondly, optically active 1,1'-bi-2-naphthol is prepared by the oxidativecoupling of 2-naphthol with (L)-(–)-α-phenylethylamine, (L)-proline and (L)-tyrolineas chiral inducing agents, and CuCl₂·2H₂O and FeCl₃·6H₂O as catalysts in severalkinds ofreaction media including water and other organic solvents for the first time.Optically active 1,1'-bi-2-naphthol is obtained with the yield of 79% and e.e. of49.4% when (L)-tyroline is used as chiral inducing agent, CuCl₂·2H₂O is used ascatalyst,and9:1(V/V) ethanolsolutionisusedas reactionmedium.Accordingtotheexperimental results ofoxidative coupling of 2-naphthol in several different reactionmedia in the presence of (L)-(–)-α-phenylethylamine and Cu(II) catalyst, we discussthe influence of reaction medium on the yield and e.e., and draw a conclusion thatoxidative coupling of 2-naphthol holds the characteristic of ion-type reaction. Inaddition, we propose a possible reaction mechanism for oxidative coupling of2-naphthol through the analysis of the configuration of the optically active productsfromtheviewpointofstereochemistry.Furthermor, several kinds of chiral transition metal complexes, which canoxidize catalytically 2-naphthol to yield optically active 1,1'-bi-2-naphthol in someorganic solvent, are synthesizedfor the first time from the corresponding derivativesofchiral amino acidand some transition metal salts, for example, CuCl, CuCl₂·2H₂O,FeCl₃·6H₂O,CoCl₂ and so on.The data show that the catalytic activity of CuCl₂–TEEcomplex, derived from (L)-tyrosine methyl ester and CuCl₂·2H₂O, andCuCl–BImpHPEA complex, derived from(1S)-(1-H-benzimidazol-2-yl)-2-(p-hydroxyphenyl)ethylamine and CuCl, are ratherhigh, and the yields are 67% and 72.6%, respectively, and e.e. are 62.1%and 53.9%,respectively. But the catalytic activity of CuCl₂–PAEE complex, prepared from(L)-phenylalanine ethyl ester and anhydrous CuCl₂, is relatively low and gives theyield of 22.4% with 44.5%e.e..N,N,N',N'-tetrabenzylethylenediamine (TBEDA) and its corresponding Cu(II)complex, bis(μ-chloro)-bis[chloro(N,N,N'-trisbenzylethylenediamine)copper(II)](Cu–TriBEDA), which comprises two similar but crystallographically independentdimeric units in crystal cell, are parpared and characterized byelemental analyses,IRspectra, ¹H NMR spectra and single-crystal X-ray diffraction. Forthermore, racemicBINOL is synthesized via oxidative coupling of 2-naphthol with Cu–TriBEDAcomplex as catalyst and molecular oxygen as oxidant.In the presence of a few amount of racemic BINOL and NaOH,BINOL-crosslinked polyacrylic acid hydrogels are prepared for the first time viafree-radical solution polymerization in water solution with K₂S₂O₈ system as initiatorand acrylic acid as monomer, and the resulting product is characterized by IRspectrum. When there is BINOL in the reaction system, free-radical polymerizationstill proceeds completely, which indicates that although being a phenol compounds,BINOL is not an efficient polymerization inhibitor, on the contrary, it can beemployed as a crosslinking agent in the polymerization of acrylic acid. The furtherstudy on the water absorbency of BINOL-crosslinked polyacrylic acid hydrogelshows that it is an efficient superabsorbent and can find a certain application in theindustry.Several versatile Mannich bases are synthesized by the regioselectiveMannich-type aminomethylation of phenol compounds such as hydroquinone and2-naphthol with morpholine, piperidine and formaldehyde (or polyformaldehyde).The corresponding reaction mechanism is proposed and the similarities anddifferences between the classical Mannich reaction and the modified Mannichreaction are summarized by the comparison between them.Finally, A family of rare earth metal complexes containing7,7,8,8-tetracyanoquinodimethane (TCNQ), Ln(phen)₄(TCNQ)₄(H₂O), are preparedand characterized by melting point, IR spectra and elemental analysis. Moreover,magnetic properties of all of Ln(phen)₄(TCNQ)₄(H₂O) complexes at roomtemperature (298 K) and Nd(phen)₄(TCNQ)₄(H₂O) complex at low temperature (5 K)are measured. The experimental results indicate that all of thoseLn(phen)₄(TCNQ)₄(H₂O) complexes are paramagnetic materials both at roomtemperature(298K)andatlowtemperature(5K).