大环化合物(macrocycles)酶模型

对大环化合物的结构特点及催化作用进行了综述。

Synthesis of Schiff Base Type Macrocycles Containing Naphthalene Ring

A series of new Schiff base type macrocyclic crown ethers containing naphthalene ring were synthesized from 2,2'-di(o-formylnaphthoxy) ethyl ether or 1,2-di(o-formylnaphthoxy) ethane and four appropriate diamines. The chemical structures of the new compounds were characterized by elemental analysis, infrared spectra, nuclear magnetic resonance spectra and mass spectrometry.

Synthesis of Novel C_2-Symmetric Chiral Polyamide Macrocycles Containing Pyridyl Side-arm

Three novel C2-symmetric macrocycles containing pyridyl units have been prepared by the cyclic condensation of chiral diamide intermediates with 2,6-pyridinedicarbonyl dichloride in highly diluted solution at room temperature.

Synthesis and Electrical Conductivities of Fully Conjugated Schiff Base Macrocycles Containing 1,3,4-Oxadiazole

Conjugated Schiff base macrocycles containing 1,3,3-oxadiazole were prepared by [2 + 2] cyclic condensation of phenylenediamine with 2,5-bis(m-formyl-phenyl)-1,3,4-oxadiazole. These macrocycles with iodine or TCNQ produced stable charge-transfer complexes. The formation of complexes were identified by UV-Vis and FT-IR spectra.

Synthesis of phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups

Novel phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups 5, 6, 7, 8 were synthesized from bishydroxyl compounds 1, 2, 3, 4 and thiophosphoryl chloride respectively. Their structures were confirmed by ^ 1H NMR, ^13C NMR, ^31p NMR and elemental analysis.

Synthesis and Mesophase Properties of Intraanular Functionized Shape-persistent Macrocycles Containing Dibenzo[fg,op]naphthacenes

On the basis of the C-C coupling reactions of dibenzo [ fg, op ] naphthacene bistriflate, which was obtained by the condensation of phenylacetates with 4-aryl-2,6-bis（2-bromo-4-methoxy-phenyl） pyrylium salts followed by palladium-catalyzed dehydrohalogenation, three shape-persistent macrocycles with dibenzonaphthacene corner pieces, a nanometer interior void, and intraanular oligoalkyl side groups were synthesized by the oxidative cyclization of the corresponding bisacetylenes under high-dilution conditions. Their thermotropic liquid crystalline properties were investigated by using polarizing microscopy and differential scanning calorimetry. All the three compounds showed nematic mesophases and belonged to discotic liquid crystals with inverted topology.

Construction of a Self-assembling Intertwined Spiral Solvent Channel Based on Interactions between Macrocycles and CH_2Cl_2

The construction of an unprecedented intertwined spiral solvent channel is driven by weak C–Cl…O and C–H…N interactions based on extraordinary parallel spirals which were structured from supramolecular synthon macrocycle 1（C44H44N4O4） with a propargylamine backbone. The product is characterized by ^1H NMR, ^13C NMR, IR and HRMS, and further confirmed by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c, with a = 28.922（3）, b = 8.5069（9）, c = 21.687（2）A^°, β = 130.6320（10）°, V = 4049.4（7） A^°3 and Z = 8. A total of 11874 reflections were collected, of which 4942 were independent（Rint = 0.0590） and 2937 were observed with I 〉 2σ（I）. The final full-matrix least-squares refinement gave R（I 〉 2s（I）） = 0.069 and w R = 0.167, S = 1.05,（Δρ）max = 0.20 and（Δρ）min =-0.22 e·A^1-3. The fluorescence of the product is discussed.

THE SYNTHESIS AND CHARACTERIZATION OF ASYMMETRIC TRIPYRRANE-CONTAINING MACROCYCLES

An improved procedure was used to prepare the asymmetric tripyrrane-containing macrocycles, The yield was over 85% These maerocycles could be oxidized to the methine bridled 23 (?)-electron aromatic cadmium(Ⅱ)complexes by reating with cadmium chloride in the presence of air and their atructures were characterized.

PHOTOPHYSICAL PROPERTIES OF THE ASYMMETRIC PENTAAZADENTATE PORPHYRIN-LIKE MACROCYCLES

The porphyrin-like macrocycles and their metal complexes are s novel family of photoresponsive molecules.The properties of the excited states,both singlet and triplet are investigated by the stationary and transient processes.

SYNTHESIS OF AZA-OXA MACROCYCLES CONTAINING PYRIDINE RING

A new type of aza-oxa macrocycles containing pyridine ring which may be used for binding of prinary ammonium cations(R-NH) were prepared from 2.6-di(bromomethyl) pyridine and appropriate diol.

Synthesis of Macrocycles Containing Amino Acid Ester and Aryl-heterocyclic Units

Four kinds of new macrocycles containing amino acids and nyl-heterocyclic units were synthesized by the condensation of di-esters containing Ts-amino acids units with di-halogenated compounds at room temperature. The macrocycles were characterized by elemental analysis, IR,MS(FAB) and 1H NMR

Studies on the Protonation and Complexations of Dioxotetraamine Macrocycles

14-Membered macrocyclic dioxotetraamines deprotonate stepwisely upon coordination to cupric ions. Singly- and doubly-deprotonated complexes are the main species, While for 13-membered analogs, non- and doubly-deprotonated complexes are the main species.

Kansuinine J,a new macrocyclic diterpenoid from the roots of Euphorbia kansui

A new macrocyclic diterpenoid,named kansuinine J（1）,was isolated from the roots of Euphorbia kansui.Its structure was characterized on the basis of spectroscopic analysis.

Characterization, crystal structure and luminescence properties of a new europium(III) complex with macrocyclic ligand derived from 2,6-diformyl-4-methylphenol and diethylenetriamine

The title compound （13,27-dimethyl-3,6,9,17,20,23-hexaazatricyclo-[23.3.1.1^11,15]-triaconta-1 （29）,2,9,11,13,15（30）, 16,23,25,27- decaene-29,30-diol-N^3, N^6, N^9, O^29, O^30）-bis （nitrato-O,O＇）-europium （Ⅲ） nitrate hydrate （[EuL（NO3）2]（NO3）·H2O, L denotes the macrocyclic ligand） was prepared and characterized by elemental analysis, infrared spectra, and electrospray mass spectra. Its crystal and molecular structure was determined by X-ray diffraction. The crystal crystallized in the monoclinic system, space group C2/c with a=2.3757 （4） nm, b=1.4302（3） nm, c=1.9584（3） nm, β=91.654（5）°, M=818.60, V=6.651（2） nm^3, Z=8, D=1.635 g/cm, F（000）=3312, R=0.0542, wR=0.1045. The central ion Eu^3＋ was nine-coordinated in the coordinaton geometry of a distorted tricapped trigonal prism. The macrocycle was coordinated through two oxygen and three nitrogen atoms. Two nitrate are chelate in the opposite positions of the macrocycle, the third nitrate being ionic. At room temperature, excitation of the title complex gave rise to the characteristic emissions of the Eu^3＋ ion.

Catalytic hydrolysis of phosphate diester (BNPP) and plasmid DNA by mononuclear macrocyclic polyamine metal complexes

The activities of the catalytic hydrolysis of phosphate diester （BNPP） [bis（p-nitrophenyl）phosphate diester] and plasmid DNA （pUC 18） by mononuclear macrocyclic polyamine metal complexes have been investigated in this paper. The results showed that the highest activity in hydrolysis of BNPP was obtained with le--Zn（II） complex （composed of lipophilic group） as catalyst. The hydrolysis rate enhancement is up to 3.64 × 10^4 fold. These metal complexes could effectively promote the cleavage of plasmid DNA （pUC18） at physiological conditions.

Synthesis and structure determination of pyrazine-containing macrocyclic polyazomethines

Two pyrazine-containing macrocyclic polyazomethines 2 and 3 were synthesized by direct [2 ＋ 2] and [3 ＋ 3] condensation reactions between 2,21-[pyrazine-2,3-diylbis（oxy）]dibenzaldehyde （1） and hydrazine. Both 2 and 3 were characterized by NMR, HRMS, and their structures were determined via X-ray crystal diffraction studies.

Heterometallic Trinuclear Ni_2Zn and Ni_2Mn Complexes of Macrocyclic Oxamide: Synthesis and Crystal Structures

Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn（NiL）2（HBTC）H2O] （1） and [Zn（NiL）2（HBTC）H2O] （2） （NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid） have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595（5）, b = 23.1498（11）, c = 17.2558（8） and =101.2530（10）°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214（8）, b = 20.6566（14）, c = 18.4126（13） and = 92.6770（10）°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.

Synthesis and Crystal Structure of a New Macrocycle Based on Diethoxycarbonyl Glycoluril: C_(26)H_(30)N_6O_(10)

A new macrocycle based on diethoxycarbonyl glycoluril 3,C26H30N6O10,has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21/c with a = 12.7291（10）,b = 25.157（2）,c = 8.5489（7） A,β = 104.4760（10）°,V = 2650.7（4） A^3,Z = 4,C26H30N6O10,Mr = 586.56,F（000） = 1232,T = 292（2） K,Dc = 1.470 g/cm^3,μ = 0.115 mm^-1,the final R = 0.0590 and wR = 0.1299 for 4918 observed reflections with I 〉 2σ（I）. In the structure of the title compound,a three-dimensional microporous architecture is formed via intermolecular hydrogen bonding interactions.

Reinvestigation on the Reaction of Salicylic Chloride with Salicylic Amide and X-ray Crystal Structure of a New Macrocyclic Polyester

The reaction of salicylic chloride and salicylic amide at 170 ℃ gave benzoxazine and a new macrocyclic polyester 3, whose crystal structure has been determined by single-crystal X-ray diffraction analysis. Compound 3: C28H16O8, Mr = 480.41, monoclinic, space group P21/n, a = 15.353(3), b = 14.196(3), c = 21.147(4) ? b = 103.32(3), V = 4485(2) ?, Z = 8, F(000) = 1984, Dc = 1.423 g/cm3 and m = 0.106 mm-1. The final R = 0.0535 and wR = 0.1275 for 7903 observed reflections (I ≥ 2(I)). In the asymmetric unit of the compound there exist two independent molecules which are connected by weak aromatic CH…O hydrogen bonding between C(47)?H(47) and atom O(7) of the carbonyl group.

The Determination of the Protonation Constants of A New Macrocyclic Dinucleating Ligand, BDBPH

The protonation constants of a new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, BDBPH, were determined by potentiometric measurement at 25.0 degreesC and mu = 0.100 mol.L-1 (KCl). The species distributions of the deprotonated and protonated compounds in the pH range from 2 to 12 aqueous solutions were also described.