New liquid crystal compounds ( )-4-[5-(2-Methylbutyl)-1,3-dioxan-2-yl]phenyl 4-alkoxybenzoate

New liquid crystal compounds, (+)-4-[5-(2-methylbutyl)-1,3-dioxan-2-yl] phenyl 4-alkoxybenzoates (5), were synthesized. The mesomorphic behaviour of these compounds is compared with that of (+)-4-(5-alkyl-1,3-dioxan-2-yl)-phenyl 4-(2-methylbutoxy)benzoates (6). While compounds 6 exhibited a chiral smectic C phase, the corresponding compounds 5 did not. This might mean that for the appearance of a chiral smectic C phase in these types of compounds, it is necessary that the carbonyl and the chiral groups exist at nearby positions. Transition temperatures to those isotropic state for compounds 5 were lower than those for compounds 6. This result is common in both cases of (+)-4-alkoxycarbonylphenyl-4-[5-(2-methylbutyl)-1,3-dioxan-2-yl]benzoates (7), and (+)-4-(2-methylbutoxy-carbonyl)phenyl 4-(5-alkyl-1,3-dioxan-2-yl)-benzoates (8).     

Synthesis and anti-inflammatory-analgesic activity of 2'',4''-difluoro-3-(carbamoyl)biphenyl-4-yl benzoates

Eighteen 2',4'-difluoro-3-(carbamoyl)biphenyl-4-yl benzoates were synthesized from diflunisal in three steps with total yields from 72% to 86%. All compounds were identified by IR, 1H NMR, MS and elemental analysis. The anti-inflammatory activity and analgesic activity for 18 compounds were evaluated. The preliminary assay results showed that compounds 4a and 4p exhibited potent anti-inflammatory-analgesic activity.     

Synthesis and pharmacological activity of 2-(biphenyl-4-yl)imidazo[1,2-a]benzimidazoles

Russian Chemical Bulletin - An efficient method for the synthesis of novel 9H-imidazo[1,2-a]benzimidazole derivatives containing a biphenyl substituent at position 2 was developed. These compounds,...     

沙库必曲中间体(R)-2-(叔丁氧羰基氨基)-3-(联苯-4-基)丙醇的合成

采用D-酪氨酸衍生物为原料,与苯磺酰氯反应制得叔丁氧羰基保护的D-苯丙氨醇苯磺酸酯,经还原,再在5 mol% N-杂环卡宾(NHC)钯催化剂(IMes)Pd(Py)Cl作用下与苯硼酸经过Suzuki-Miyaura偶联反应得到沙库必曲重要中间体(R)-2-(叔丁氧羰基氨基)-3-(联苯-4-基)丙醇,总产率大于57%,ee值大于99%。     

Synthesis and Crystal Structure of (S)-N-(2-oxoazepan-3-yl)biphenyl-4-carboxamide

The title compound(S)-N-(2-oxoazepan-3-yl)biphenyl-4-carboxamide(C19H20N2O2, Mr = 308.37) was synthesized by the reaction of(S)-α-amino-∑-caprolactam with 4-phenyl-benzoyl chloride. Its chemical structure was determined by 1H NMR, 13 C NMR, H RMS and X-ray single-crystal diffraction. The crystal belongs to the triclinic system, space group P1 with a = 8.2650(17), b = 13.774(3), c = 15.109(3) ?, β = 90.20(3)o, V = 1645.6(6) ?3, Z = 4, Dc = 1.245 g/cm3, μ = 0.081 mm-1, F(000) = 656, R = 0.0756 and w R = 0.1491 for 5964 observed reflections with I 2σ(I). The title compound was also used to prepare polyamide.     

4′-(2-(2-Ethoxyethoxy)ethoxy)biphenyl-4-carboxylic acid—a polar smectogen for amphipathic liquid crystals

We describe a new calamitic smectogen and some of its esters with a three-block molecular architecture (polar oxyethylene chain, rigid biphenyl and non-polar aliphatic chain) which were characterised by a combination of optical, thermical, X-ray and computational techniques. The title compound is a valuable smectogenic building block for amphipathic functional organic materials.     

Influence of spacer variation on phase behaviour of liquid crystalline copolymethacrylates containing cholesteryl and S-(-)-4-chloropropionyloxybiphenyl-4-yl groups

Liquid crystalline side group copolymers containing cholesteryl and S-(-)-chloropropionyloxybiphenyl groups were synthesized and investigated by size exclusion chromatography, 1H NMR spectroscopy, polarization microscopy, X-ray diffraction and differential scanning calorimetry. The spacer of the cholesteryl-containing side groups was changed by the substitution of two methylene groups by ether groups. The existence of a cholesteric phase on copolymerization of two monomers containing chiral tail groups, from which the homopolymers exhibit only smectic phases, could be observed. This cholesteric phase only exists over a narrow range of copolymer composition. The temperature dependence of the reflection wavelength for the cholesteric phase was determined. For the cholesteryl-containing homopolymer, an SA bilayer phase was observed, whereas the S-(-)-chloropropionyloxybi2 phenyl homopolymer showed a higher ordered SB phase below an SA monolayer phase. The layer periodicities of the SA phases of the copolymers depend on the composition. The substitution of two methylene groups of the spacer by ether groups led to disappearance of the cholesteric phase. Simultaneously, over a small range of copolymer composition a biphasic region was obtained.     

Highly efficient yellow-emitting iridium(III) complexes based on fluorinated 2-(biphenyl-4-yl)-2H-indazole ligands: Syntheses,structures, properties,and density functional theory calculations

Two new iridium (III) complexes ( Ir1-Ir2 ) bearing different fluorinated 2-(biphenyl-4-yl)-2H-indazole-based compounds as cyclometalated ligands and Xantphos as an ancillary ligand were synthesized and fully characterized. The ultraviolet (UV)–vis absorption, photoluminescence, and electrochemistry properties were studied. The single crystal structures of Ir1-Ir2 were determined by X-ray diffraction, showing each adopts the distorted octahedral coordination geometry. To gain insights into the lowest energy electron transitions and the lowest triplet excited states, density functional theory calculations were used to further investigate the origination. Two complexes emit yellow photoluminescence with quantum yields of 49.7–72.5% in solution at room temperature. Their Commission Internationale de L'Eclairage color coordinates are (0.42, 0.53) and (0.39, 0.47), respectively.     

Synthesis,film-forming properties,and photosensitivity of 4-alkoxy(acyloxy)-3-alkoxyphenylmethylene-(biphenyl-4-yl)amines

The reactions of ethers and esters of the vanillin series with biphenyl-4-ylamine in absolute methanol yielded previously unknown E isomers of biphenyl-substituted azomethines (Schiff bases). The film properties and photosensitivity of the new compounds were examined.     

Synthesis and anti-inflammatory-analgesic activity of 2′,4′-difluoro-3-（carbamoyl）biphenyl-4-yl benzoates

Eighteen 2′,4′-difluoro-3-（carbamoyl）biphenyl-4-yl benzoates were synthesized from diflunisal in three steps with total yields from 72% to 86%. All compounds were identified by IR, 1^H NMR, MS and elemental analysis. The anti-inflammatory activity and analgesic activity for 18 compounds were evaluated. The preliminary assay results showed that compounds 4a and 4p exhibited potent anti-inflammatory-analgesic activity.     

Synthesis of 3-[5-(biphenyl-4-yl)pyrrol-2-yl]-1-phenylprop-2-yn-1-ones by palladium-free cross-coupling between pyrroles and haloalkynes on aluminum oxide

Cross-coupling of 2-(biphenyl-4-yl)pyrroles derived from 1-(biphenyl-4-yl)ethanone oximes and acetylene with 3-bromo-1-phenylprop-2-yn-1-one on aluminum oxide gave 3-[5-(biphe-nyl-4-yl)pyrrol-2-yl]-1-phenylprop-2-yn-1-ones in 35–46% yields.     

The synthesis and liquid crystalline behaviour of 2-(4-n-alkoxyphenyl)-5-methylpyridines

We have synthesized a new series of polyphenylene compounds with a pyridine ring, 2-(4-n-alkoxyphenyl)-5-methylpyridines (CH₃C₅H₃NC₆H₄OC _i H_2i1) (1a-i ; the carbon number, i, of the alkoxy group is 1-9), and studied their phase transitions and mesogenicity using DSC and polarizing microscopy. In the homologous series of 1a-i , no mesomorphic phase appeared for i=1-5 and only a monotropic nematic phase was observed for i=6-9. The mesomorphic potential is relatively weaker for the 1a-i than for the 2a-i and 3a-i homologues, which are pyridine-containing three- and four-ring similar systems. This lowering of the mesogenicity may be due to the lack of a phenyl ring between the pyridine ring and the methyl group in the 1a-i homologues.     

Synthesis of 6-Methyl-4-(1-methyl-2-buten-1-yl)-2-(2-cyclohexen-1-yl)- and 6-Methyl-4-(1-methyl-2-buten-1-yl)-2-(1-cyclohexen-1-yl)anilines

Alkenylation of 6-methyl-2-(2-cyclohexen-1-yl)- and 2-(1-cyclohexen-1-yl)anilines with piperylene in the presence of AlCl₃ and transformation of the resulting cyclohexenylanilines into carbazole structures were studied.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 3, 2005, pp. 441–443.Original Russian Text Copyright © 2005 by Gataullin, Ishberdina, Sotnikov, Abdrakhmanov.     

New copper(II) coordination compounds with 1,3-bis(5-(pyridin-2-yl)-1,2,4-triazol-3-yl)propane

Two new copper(II) complexes with 1,3-bis(5-(pyridin-2-yl)-1,2,4-triazol-3-yl)propane (H₂L), [Cu₂(HL)Cl₃] · H₂O (I) and [Cu(H₂L)](ClO₄)₂ (II), were described. The compounds were characterized by elemental analysis, IR spectroscopy, and magnetochemical data. According to X-ray diffraction data (CIF files CCDC nos. 1497511 (I), 1497512 (II)), complex I is binuclear and the metal cations are bound by the nitrogen atoms of the triazole ring and by the chloride anion. Complex II is mononuclear. Analysis of the temperature dependence of the magnetic susceptibility of I attests to the antiferromagnetic coupling of paramagnetic centers (–2J = 18 cm^–1). Exchange channels are analyzed by means of density functional theory (B3LYP/6-311G(d)) using the broken symmetry approach.     

The synthesis and liquid crystalline behaviour of 2-(4-n-alkoxyphenyl)-5-methylpyridines

We have synthesized a new series of polyphenylene compounds with a pyridine ring, 2-(4-n-alkoxyphenyl)-5-methylpyridines (CH₃C₅H₃NC₆H₄OC_iH_2i1) (1a-i; the carbon number, i, of the alkoxy group is 1-9), and studied their phase transitions and mesogenicity using DSC and polarizing microscopy. In the homologous series of 1a-i, no mesomorphic phase appeared for i=1-5 and only a monotropic nematic phase was observed for i=6-9. The mesomorphic potential is relatively weaker for the 1a-i than for the 2a-i and 3a-i homologues, which are pyridine-containing three- and four-ring similar systems. This lowering of the mesogenicity may be due to the lack of a phenyl ring between the pyridine ring and the methyl group in the 1a-i homologues.     

Crystal Structure and Theoretical Energy Gap of 2-(2-((4-(Pyridin-2-yl)pyrimidin-2-yl)disulfanyl)pyrimidin-4-yl) pyridinium Hexafluorophosphate

The crystal structure of 2-(2-((4-(pyridin-2-yl)pyrimidin-2-yl)disulfanyl)pyrimidin-4-yl)pyridinium hexafluorophosphate was obtained by X-ray single-crystal diffraction. This molecule crystallizes in monoclinic P2/c space group with a=6.219(1), b=13.103(2), c=13.059(2) ?, β=97.567(2)°, Z=2, the final R=0.0525 and w R=0.1434. The title compound was prepared successfully from 1,2-bis(4-(pyridin-3-yl)pyrimidin-2-yl)disulfane(BPPD). TD-DFT computational studies on energy gaps and UV-Vis spectra of BPPD and the title compound have been carried out for comparisons. The resultant HOMO-LUMO gap of the BPPD compound is 4.45 e V, while that for the corresponding hexafluorophosphate salt is much smaller at 2.46 e V, which are in agreement with their UV-Vis absorptions.     

New 1-(2-chloroquinolin-3-yl)-4-dimethylamino-2-(naphthalen-1-yl)-1-phenylbutan-2-ols with antituberculosis activity

Russian Chemical Bulletin - New 4-dimethylamino-2-(naphthalen-1-yl)-1-phenyl-1-(quinolin-3-yl)butan-2-ols with antituberculosis activity were synthesized....     

Synthesis of Geminally Activated 4-(Furan-2-yl)- and 4-(Thiophen-2-yl)-1-nitrobuta-1,3-dienes

The condensation of 3-(furan-2-yl)- and 3-(thiophen-2-yl)prop-2-enals with nitro-substituted CH acids, namely ethyl nitroacetate, nitroacetone, nitroacetophenone, and nitroacetonitrile, afforded a series of geminally activated nitro dienes, 4-(furan-2-yl)- and 4-(thiophen-2-yl)-1-nitrobuta-1,3-dienes. The product structure was confirmed by NMR and IR spectroscopy.

     

Nitrilimine cycloaddition to 4-(pyrazol-5-yl)carbonyl-2-azetidinone and 4-(pyrazol-4-yl)carbonyl-2-azetidinone

The higly stereoselective nitrilimine cycloaddition onto the novel 3(R*)-phenyl-4(S*)-cinnamoyl-2-azetidinone 2 gave 4-(4,5-dihydropyrazol-5-yl)carbonyl-2-azetidinone 5 as the major product and 4-(4,5-dihydropyrazol-4-yl)carbonyl-2-azetidinone 6 as the minor one. Ceric ammonium nitrate (CAN) oxidation of the cycloadducts gave the title compounds with good overall yield.     

study of liquid crystalline N -[4-(4- n -alkoxybenzoyloxy)-2-hydroxybenzylidene]methylanilines

New homologous series of N-[4-(4-n-alkoxybenzoyloxy)-2-hydroxybenzylidene]methylanilines [nAHmM(n=1-8/10; m=2: ortho, m=3: meta, m=4: para)] were synthesized. They exhibited a nematic phase except for 1AH3M. The temperature dependence of their Raman spectra was observed in the spectral range of 900–1700 cm^-1. In one group of nAHmM compounds, the Raman band at about 1360 cm^-1 abruptly decreased in intensity and wavenumber when the crystalline solid-liquid crystal phase transition was approached. In another group, the corresponding band increased through the phase transition. The bands have been assigned to the coupling mode between the in-plane CCH deformational vibration and the ring-N stretching vibration. Such a behaviour can be explained by the molecular conformation with different twist angles of the aniline ring in relation to the Schiff's base plane of the molecule. Some nAHmMs exhibited photochromism.