6,6-Di-C-alkyl-d-galactopyranoses. A new group of liquid crystalline compounds forming columnar phases [1]

The geminally C-branched 6,6-di-C-n-alkyl-d-galactopyranoses 3a-d prepared in two steps from 1,2:3,4-di-O-isopropylidene-d-galacturonic acid methylester 1 and the even numbered C₈-C₁₂-alkylmagnesium bromides, represent a new group of 'double tailed' thermotropic mesogens forming columnar supramolecular structures based on hydrogen bridged (disc-like) multimers in accordance with the hypothesis of the Praefcke group. Furthermore, the thermal behaviour of the homologous 6-O-alkyl-d-galactopyranoses 4a-e is discussed in connection with the revised model for the molecular arrangement in smectic A phases of 'single tailed' carbohydrates.     

Synthesis and thermal properties of mesomorphic 1,1'-bis[ω-(4'-cyano-4-biphenyloxy)alkyl] ferrocenes

A new series of 1,1'-disubstituted ferrocene compounds of the type [(η⁵-C₅H₄(CH₂)_nOC₆H₄C₆H₄CN]₂Fe (3a-d, n = 5, 6, 8, 11) incorporating a variable length alkyloxy cyanobiphenyl unit has been prepared and their mesomorphic properties have been investigated. Compounds 3b, c and d exhibit a thermotropic smectic C phase and 3c also exhibits a monotropic smectic A phase over a fairly wide range near ambient temperature.     

Synthesis and mesomorphic properties of new liquid crystalline compounds VIII. Indolinobenzospiropyranyl aryliminobenzoates

A series of new liquid crystalline compounds, indolinobenzospiropyranyl aryliminobenzoates, 1a-d, have been synthesized and their mesomorphic properties characterized. Analysis by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction showed that the benzoates 1a and 1d form a monotropic mesophase, whereas 1b and 1c show an enantiotropic mesophase. Enantiomorphic properties are uncommon to spiropyran-containing LC molecules. Among the compounds investigated, 1a was found to exhibit a monotropic SmC phase between 90 and 79°C.     

CONDENSATION REACTION OF α-AROYL-α-ACETYL KETENE CYCLIC DITHIOACETALS WITH AROMATIC ALDEHYDES

As a versatile three-carbon syntho,α-oxoketene cyclic acetals 1 have been applied in many fields. In order to study the structure and application of 1, we performed that α-aroyl-α-acetyl ketene cyclic dithioacetals 2 or 3 condensed with aromatic aldehydes catalyzed by sodium ethoxide and fifteen new condensation products 4 and 5 were obtained.     

Preparation of silybin 23-esters ability against LPO and and evaluation of their inhibitory DNA protective properties

Twelve 23-esterified silybin derivatives with different patterns of substituents such as aromatic and aliphatic groups (1-12) were designed and synthesized. The antioxidative properties of these compounds were evaluated. The modified silybin analogues exhibited improved inhibitory effects against rat liver homogenate lipid peroxidation compared to silybin, with exception of the trimethoxylated ester (5) and the aliphatic one (9). Compounds 3, 5, 7, 8 and 11 displayed their protective properties on DNA cleavage in a dose-dependent manner.     

Two New Borates Built by Different Types of {B9} Cluster Units

Two new belt-like borates Na₄[B₉O₁₄(OH)₃]·0.5H₂O(1) and Na₅[B₉O₁₄(OH)₄](2) have been synthesized under solvothermal conditions. Both compounds contain unprecedented B₉O₁₆(OH)_n^(n+5)-[n=3(1), 4(2)] clusters, which are constructed from four B₃O₃ rings via three BO₄ tetrahedra. Compound 1 exhibits a rare 1D belt with two types of 8-membered ring(MR) windows based on B₉O₁₆(OH)₃^8- clusters. Compound 2 features two different 1D belts built by different B₉O₁₆(OH)₄^9- units, which is first discovered in borate family. UV-Vis diffuse reflectance spectra reveal that compounds 1 and 2 have the cut-off edges below 190 nm, indicating that they may have potential application in deep UV(DUV) region.     

Liquid crystalline photoconductors

The influence of molecular order as well as of orientation of charge carrier units on photoconductivity has been investigated for the liquid crystal photoconductors H5T (1), thiadiazole (2) and oxadiazole (3). The discotic H5T (1) and both smectic systems 2 and 3 exhibit a higher photocurrent in the highly ordered mesophase than in the polycrystalline or isotropic state. For 1, results concerning charge carrier transport mechanism and Dember effect are given indicating an electronic charge transport comparable with the one known for single crystalline anthracene.     

Novel Enone-benzene Rearrangement of 4,4-Dialkylcholest-5-en-3-ones to Ring-B Aromatic Steroidal Hydrocarbons Catalysed by p-Toluenesulfonic acid

Under acidic conditions, α,α-dimethyl-β,γ-unsaturated cyclohexanones undergoes an enone-benzene rearrangement leading to aromatic derivatives^1-4. We recently run an enone-benzene rearrangement of 4,4-dimethyl-cholest-5-en-3-one (1a) catalysed by montmorillonite K-10 to give 1,3,4-trimethyl-19-norcholesta-1,3,5(10)-triene (2a) in moderate yield accompanying intractable mixture of hydrocarbons as by products⁵. Repetition of this reaction by employing TsOH as a catalyst, 2a was obtained in 65% yield and a new product, 6-methyl-3-isopropyl-A,19-dinorcholesta-6,8,10(5)-triene (3a), was also isolated in 25% yield. The formation of 3a has not been reported in earlier studies^1-5. Herein we report the novel enone-benzene rearrangement of 4,4-dialkylcholest-5-en-3-ones (1a~d) leading to ring-B aromatic steroidal hydrocarbons (3a~d) catalysed by TsOH (Scheme 1).     

Polyoxygenated anti-inflammatory biscembranoids from the soft coral Sarcophyton tortuosum and their stereochemistry

Five novel biscembranoids,ximaolides H-L(1-5),along with four known related compounds(6-9) were isolated from the Hainan soft coral Sarcophyton tortuosum.The structures of the new compounds were determined by extensive spectroscopic analysis,quantum chemical calculations,and/or by comparing their CD spectra with those of the known compounds.Compounds 1 and 2 are the first examples of biscembranoids bearing a 1,35-bridged lactone moiety,4 is the first biscembranoid comprising an uncommon oxetane ring,and 5 represents the first 36-peroxyl biscembranoid.Ximaolides Ⅰ(2),K(4) and F(9) exhibited interesting anti-inflammatory activity by the inhibition of LPS-induced TNF-α protein release in RAW264.7 macrophages.     

Liquid crystalline properties of dissymmetric molecules VI. The effect of alkyl chain length on molecular arrangement in the smectic A phase in three-aromatic-ring systems with two ester groups

The effect of alkyl and alkoxy chain lengths on the layer structures of smectic A and C phases has been examined by X-ray diffraction measurements on three isomeric systems: 4-alkoxyphenyl and 4-n-alkylphenyl 4-[(4-octyloxyphenyl)carbonyloxy]benzoates (1); 4-octyloxyphenyl 4-[4-(octyloxyphenyl)carbonyloxy]benzoates (2); 4-octyloxyphenyl, 4-alkoxyphenyl and 4-n-alkylphenyl terephthalates (3); and p-phenylene 4-octyloxybenzoates, 4-alkoxybenzoate and 4-n-alkylbenzoate (4). Although all the derivatives exhibit smectic A and/or C phases having a monolayer arrangement of the molecules, the layer spacings are considerably affected by alternation of the ester linkages. The layer spacings for the homologues of 1 are a little shorter than the calculated molecular lengths, while those for 2 agree with the calculated molecular lengths. The layer spacings for 3 show a notable even-odd alternation in the higher homologues. The results are discussed in terms of a subtle change in the molecular structures due to replacement of the ester groups.     

Investigation of the crystal structure of two amphiphilic diols

The crystal and molecular structures of (R)-4'-(2,3-dihydroxypropyloxy)-4-cyanobiphenyl, 1 and 4'-(cis-cis-3,5-dihydroxycyclohexyloxy)-4-cyanobiphenyl, 5 have been determined. The packing of compound 1 occurs in sheets, with a dense hydrogen bonding network within the layer of one sheet and to the next sheet, whereby the cyano groups are incorporated into the hydrogen bonding network. The hydrogen bonding scheme of compound 5 involves a water molecule; there is some disorder with regard to the hydrogen atoms bound to the water molecules.     

First Total Synthesis of (±)-Ponganone Ⅲ

In recent years, the synthesis and pharmacology of pyranoflavanoids have been extensively investigated due to their wide range of pharmacological properties^[1-3]. Ponganone Ⅲ^[4],a new natural pyranoflavanone isolated from the Pongamia pinnala, was identified as (2S)-3',4'-dimethoxy-6',6"-dimethylpyrano-[2",3":7,8]-flavanone (2) on the basis of spectra data. Its precursor,3,4-dimethoxy-2'-hydroxy-6",6"-dimethylchromeno-[2",3":4',3']-chalcone (1) is also a new natural product^[5] isolated from the roots of Lonchocarpus subglaucescent. Their total synthesis have not been reported. Herein, we wish to report the first total synthesis of compounds 1 and 2 in order to confirm the proposed structure and further more to evaluate its biological activities.     

A novel cytotoxic neophysalin from Physalis alkekengi var.francheti

A new neophysalin,named 5α-hydroxy-25,27-dihydro-4,7-didehydro-7-deoxyneophysalin A(1),along with three other known neophysalins(2-4) were isolated from the calyxes of Physalis alkekengi L.var.francheti(Mast.) Makino.The structure of 1 was determined by means of 1D and 2D NMR,UV,IR and mass spectra.Compound 1 displayed potent cytotoxicities in vitro against PC- 3 and LNCaP cell lines.     

Synthesis and characterisation of main-chain hydrogen-bonded supramolecular liquid crystalline complexes formed by azo-containing compounds

A series of azopyridine-containing hydrogen bonding acceptors (4a-c) with flexible spacers of oligo(methylene) were synthesised. Hydrogen-bonded polymeric complexes 4/5 and trimeric complexes 4/6₂ , where 5 and 6 are aromatic dicarboxylic acids and monocarboxylic acids, respectively, were prepared and their liquid crystallinity was examined using differential scanning calorimetry and polarising optical microscopy. The study showed that most of the complexes displayed reversible thermotropic nematic phase. The isotropic to nematic phase transition temperatures of polymeric complexes 4/5 and trimeric complexes 4/6₂ in general decreased with the increase in length of spacers and terminal groups in the corresponding proton acceptors 4 and the proton donors 5 and 6, respectively. Hydrogen bonding interactions in complexes 4/5 and 4/6₂ were studied by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy.     

Evaluation of carborane-containing nematic liquid crystals for electro-optical applications

Three new structurally similar compounds in series 1[2] and 2 containing 12- and 10-vertex p-carborane units (A and B) were prepared. Their thermal properties were investigated in the pure state and compared to those of their carbocyclic analogues. Using several higher homologues in the series 1[n], clearing temperatures for the unknown 1[4] and 1[10] were predicted. Optical, dielectric and rotational viscosity parameters for carborane derivatives 1[2] and 2 and their cyclohexane analogies were obtained by extrapolation of values measured for 10% solutions in a standard nematic host. The observed trends were rationalised using computed molecular parameters.     

On the molecular and mesophase structures of disc-like tetrapalladium liquid crystals

Various members of two series of μ-halogeno-bridged tetrapalladium mesogens each with twelve dodecyloxy chains, but differing in the size of their large disc-like macroheterocyclic cores, 1 a-e and 2a-c, as well as one new short-chained homologue (1 c') of one of the series, as a model compound for single crystal X-ray studies, are presented. Our results on that model compound again unambiguously confirm earlier statements about the unique molecular structure of the core of these flat tetrapalladium complexes. The properties of all thermomesogenic compounds have been studied by differential scanning calorimetry, polarizing microscopy, and also by X-ray diffraction; the latter method reveals an oblique arrangement of disordered columns in most of the mesophases exhibited by the members of both series 1 and 2.     

Theoretical Studies on Copper,Nickel Complexes of Corrole and Isocorrole

Corrole 2, an analogue of porphyrin 1, is also a fascinating molecule. It can be considered as an intermediate in the biosynthesis of corrin 3,the chromophore of Vitamin B₁₂, Similar to porphyrin, corrole also has 18 electrons in the π-system of the ring and is aromatic. Recently, isocorrole 4, another compound in the corrole family, was synthesized by Vogel's group^[1].One important feature of corrole and isocorrole is the possible formation of tri-anion, and thus the ability to stabilise high-oxidation-state metal cations.     

Regioselective Synthesis of Two Novel 2-geranyloxyacetophenones

The phenols containing geranyl units¹ are a large group of interesting natural products exhibited many physiological actions as antiflammatory, antibacterial and antioxidative activities². Two novel acetophenones 1 and 2 were recently isolated from the fruits of Evodia merrillii, a small folk medicinal tree widely distributed in Taiwan³. Their structures were elucidated as 2-(1'-geranyl)-4,6-dihydroxyacetophenone 1 and 2-(1'-geranyloxy)-2,6,α-trihydroxyacetophenone 2 by means of spectroscopic data. So far as we know, the total synthesis of them have not been reported yet. Herein, we wish to report the first total synthesis of 1 and 2,starting from 2,4,6-trihydroxyacetophenone.     

Anionic Cyclization Approach to Hexahydrobenzo[b] furan-3-one and Hexahydro-1H-3-indolone:Application to Total Syntheses of Natural Products

Hexahydrobenzo[b]furan-3-one(3) and hexahydro-1H-3-indolone (4) are potentially useful intermediates for total synthesis of natural products, such as the hexahydrobenzofuran unit (5) of avermectins and pancracine (6). Anionic cyclization approach toward (3) and (4) have been developed. Their application to the total synthesis of (5) and (6) will be presented.