Dependence of selective enclathration on types of cholic acid crystals

Competitive recrystallizations of cholic acid (CA) from 1:1 binary mixtures of seven mono-substituted benzenes are demonstrated. The order of preference for guests to be incorporated into the cholic acid crystals are as follows: benzene, toluene > n-amylbenzene, n-hexylbenzene > ethylbenzene, n-propylbenzene, n-butylbenzene. These seven compounds afford bilayer type inclusion crystals that are classified into four types based on the host frameworks and host-guest stoichiometries. The order of selective enclathration corresponds to the four types as follows: 1:1 alpha G > 2:1 alpha G > 1:1 beta T or 2:1 alpha T. The preference for the alpha G type was also confirmed by investigating the host frameworks of the crystals obtained from binary mixtures. The dependence of the selectivity on the different types of CA crystals can be understood in terms of the fit of the guest molecule in the host cavity.     

Continuous hydrogenation reactions in a tube reactor packed with Pd/C

Continuous flow of the substrate solution and hydrogen gas through a tube reactor packed with Pd/C catalyst brings about a highly reactive and efficient hydrogenation system, which converts 4-cyanobenzaldehyde to the benzyl alcohol derivatives at 25 degrees C, and at 90 degrees C, the cyano group becomes reduced to give the corresponding amine and toluene derivatives within 2 min.     

Organic intercalation material: reversible change in interlayer distances by guest release and insertion in sandwich-type inclusion crystals of cholic acid

Cholic acid (CA) forms inclusion crystals that have a sandwich-type lamellar structure constructed by the alternative stacking of host bilayers and guest layers. Five disubstituted benzenes, o-toluidine, m-fluoroaniline, o-chlorotoluene, o-bromotoluene, and indene, are accommodated in the two-dimensional void space between the host bilayers at 1:2 host-guest stoichiometries. Thermal gravimetric analysis of the inclusion crystals revealed that all the guest molecules, except o-toluidine, are released in two separate steps, indicating the formation of intermediate crystals after the first guest release. Adequate heat treatment of the four inclusion crystals induces release of half or three quarters of the guest molecules. X-ray diffraction patterns of the intermediate crystals revealed that the crystals have a bilayer structure the same as those of the common CA inclusion crystals. They have one-dimensional cavities, in which the guest molecules are included at a 1:1 or 2:1 host-guest stoichiometry. These facts indicate that the host bilayers move 1.6-4.5 A perpendicular to the layer direction by desorption of the guest molecules. Furthermore, a reverse structural change is also achieved by absorption of the guest molecules to regenerate the starting sandwich-type inclusion crystals. This reversible change in the host bilayer by the guest sorption and desorption is a novel example of organic intercalation materials.     

Relationship between Separation Behavior and Structural Flexibility in Inclusion Crystal of Cholic Acid

Selective incorporation of two aromatic compounds, benzene and ethylbenzene,into an inclusion crystal of cholic acid was investigated. Addition of an excessamount of 1:1 mixture of benzene and ethylbenzene into saturated solution ofcholic acid in 1-butanol led to a spontaneous formation of an inclusion crystal.The co-crystal contained benzene and ethylbenzene at the constant molar ratioof 8:2 irrespective of the relative concentrations of guest and host in the feedsolution, indicating that the resulting crystal consists of the two guests mixedin a single host framework. The resulting ternary crystal had thermal behaviorsimilar to a binary crystal obtained from benzene. In contrast to the guest/hostratio, the benzene/ethylbenzene ratio in the feed solution affected that in theinclusion crystal. Benzene was basically preferred in the cholic acid crystalover ethylbenzene, but the selectivity reversed at an excess amount of ethylbenzene.This separation behavior can be understood in terms of the structural flexibility ofhost frameworks.