Synthesis And Separation Of Spiro-Compounds With Chiral Axes

Chiral compounds were widely used in pesticides, hormone, food additives, and physiologically active amino acids and alcohols, especially in medicines. Since the 1990s, the research of the chiral pharmaceuticals has become the strategic direction and hot area in the development of the new medicines. There are mainly three methods for synthesizing chiral medicines: extraction from natural products, separation and synthesis by asymmetrical catalysis. At present the most widely used method is the last one. That is to synthesize chiral medicines by chiral technique, which is the most studied method for preparing single chiral compounds recently.In this dissertation, a series of chiral spiro compounds were prepared by contrapuntal substituted benzaldehyde and pentaerythritol, and in which 5 compounds were separated by HPLC, crystallizing and chemical method. It was as follow:1. 4,4'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dibenzaldehyde and 7 other spiro compounds were prepared by对位substituted benzaldehyde and pentaerythritol, and the effects of different conditions like solvents and catalyst were studied;2. Separation of four compounds were tried by HPLC, and 3,9-dip-tolyl-2,4,8,10- tetraoxaspiro[5.5]undecane was successfully separated with the hexane and iso- propanol (98:2) as mobile phase.3. 4,4'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dibenzonitrile was separated by reacting with (8R,9S)-(+)-N-benzylcinchonin chloride, and 4,4'-(2,4,8,10-tetraoxaspiro[5.5] undecane-3,9-diyl)dibenzoic acid was separated by L-phenylethylamine. The optical rotations were measured as well.4. A novel dendrimer 9H,9H,11H,11H,12H,12H-hexahydrobenzo[9,10]-1H,1H,3H,3H, 4H,4H,5H,5H,7H,7H,8H,8H-dodecahydrophenanthrene-2,6,10-trioneketal-tri-(4-(4-(3-(9-(4-(2,6-disulfo-cyclohexyl)phenyl))-2,4,8,10-tetra-oxa-spiro[5.5]undecyl))phenyl-1,1-(2,6-dioxa)cyclohexanedimethanol was conveniently synthesized by the reaction of hexahydrobenzo [9,10]dodecahydrophenanthrene-2,6,10-trione ketal-tri-2,2-dihydromethyl-1,3-propanediol with 4-(4-(3-(9-(4-(2,6-disulfo-cyclohexyl)phenyl))-2,4,8,10-tetra-oxa-spiro[5.5]undecyl)) phenyl-1,1-(2,6-dioxa)cyclohexanedimethanol.