Structural characterization and mass spectrometry fragmentation signatures of macrocyclic alkanes isolated from a Sydney Basin torbanite,Australia

Individual hydrocarbons identified to be macrocyclic alkanes in a torbanite from the Sydney Basin(Australia)were successfully isolated from its extracts using preparative gas chromatography and analyzed by NMR.Saturated cyclic structures were confirmed by single peaks in the NMR~1H and~(13)C spectra indicating single forms of H and C atoms exist in these biomarker molecules.This is consistent with the methylene unit in a ring system assignment of the macrocyclic alkanes and accounts for a formula of(CH2)n.The unusual molecular structures of these compounds are consistent with those that were identified from previous GC retention index data and co-injection with a standard supports the previous research.The mass spectral fragmentation behaviors of representative cyclic alkanes were further investigated by comparing them with the mass spectra of isolated individual macrocyclic alkanes.The characteristic fragment ions in the macrocyclic alkanes of(M–28)+and base peaks of m/z 97,111,125,etc.,can be assigned as being generated by simple a-/i-cleavage and hydrogen rearrangement.These fragmentation pathways combined with retention indices should assist in differentiating these compounds from monounsaturated alkenes and alkylated monocyclics having similar mass spectral characteristics in other geological samples.

Synthesis and spectral studies of macrocyclic Pb(Ⅱ),Zn(Ⅱ),Cd(Ⅱ)and La(Ⅲ) complexes derived from 1,4-bis(3-aminopropoxy)butane with metal nitrate and salicylaldehyde derivatives

Eight new macrocyclic complexes were synthesized by template reaction of 1,4-bis（3-aminopropoxy）butane with metal nitrate and 1,3-bis（2-formylphenyl）propane or 1,4-bis（2-formylphenyl）butane and their structures were proposed on the basis of elemental analysis, FTIR, UV-vis, molar conductivity measurements, ^1H NMR and mass spectra. The metals to ligand molar ratios of the complexes were found to be 1： 1. The complexes are 1：2 electrolytes for Pb（II）, Zn（II） and Cd（II） complexes and 1：3 electrolytes for La（III） as shown by their molar conductivities （Am） in DMSO at 10^-3 mol L^-1. Due to the existence of free ions in these complexes, such complexes are electrically conductive. The configurations of La（III） and Pb（II） were proposed to probably octahedral and Zn（II） and Cd（II） complexes were proposed to probably tetrahedral.

Synthesis of Arsamacrocyclic Polyethers

The synthesis of eight new arsamacrocyclic Polyethers was described. The structures of these compounds were characterized by elemental analysis, IR, H-1-NMR and MS.

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.

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.

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.

CLEMOCHINENOSIDE A, A MACROCYCLIC COMPOUND FROM CLEMATIS CHINENSIS

The structure of a new macrocyclic compound, clemochinenoside A obtained from Clematis chinensis was identified by NMR, FAB-MS, NOE and chemical hydrolysis.

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.

Synthesis and Characterization of Two Binuclear Macrocyclic Zinc(Ⅱ) Complexes by Anion Exchange

Two macrocyclic zinc（Ⅱ） complexes {[ZnL（VO3）2]·0.33H2O}n（1） and [ZnL（H2O）2][Ni（CN）4]（2）（L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane） have been obtained from the reactions of [ZnL]（ClO4）2 with NH4VO3 and K2[Ni（CN）4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn（Ⅱ） atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2＋, forming one-dimensional channels occupied by guest water molecules. The monomers of [ZnL（H2O）2]2＋ and [Ni（CN）4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.

The Synthesis of a New Macrocyclic Dinucleating Ligand,3,6,9,17,20,23-Hexaaza-29,30-Dihydroxy-13,27-Dimethyl-Tricyclo[23,3,1,1^(11,15)]Triaconta-1(28),11,13, 15(30),25,26-Hexaene

A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesized by the NaBH4 reduction of the Schiff-base obtained from the [2+2] condensation between diethylenetriamine and diformyl -p-cresol. The structure was characterized by elemental analysis, 1HNMR and FAB-MS. The synthetic method was also discussed.

Chiral Resolution of β-dl-Phenylalanine Using Chiral Macrocyclic Nickel(Ⅱ) Complexes

The reactions of chiral four-coordinated nickel（Ⅱ） complex [Ni（RR-L）]（ClO4）2/[Ni（SS- L）]（ClO4）2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni（RR-L）（β-d-HPhe）]（ClO4）2（1） and [Ni（SS-L）（β-l-HPhe）]（ClO4）2（2）, respectively（L = 5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, HPhe = phenylalanine）. Single-crystal X-ray diffraction analyses revealed that the nickel（Ⅱ） atom displays a distorted octahedral coordination geometry by coordinating with four nitrogen atoms of L in a folded configuration, and two carboxylate oxygen atoms of β-d/l-HPhe in cis-position in both complexes. The monomers of [Ni（RR-L）（β-d-HPhe）]2＋ and [Ni（SS-L）（β-l-HPhe）]2＋ are connected through intermolecular hydrogen bonds to generate one-dimensional zigzag chains, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.

Synthesis of macrocyclic lactones with methoxysulfonyl side chain

Two representative macrocyclic lactones with methoxysulfonyl side chain（5a and 5b）were synthesized employing Michael addition with acrolein and ring enlargement as the key steps,starting from potassium,α-oxocycloaikylsulfonates（1）in total yields of 45 and 57%,respectively.

Synthesis of aromatic-linked polyamine macrocyclic derivatives as HIV-1 entry inhibitors

A series of novel aromatic-linked polyamine macrocyclic derivatives have been synthesized. Their structures were confirmed by MS and ^1H NMR. These compounds exhibited potent anti-HIV-1 activities.

Synthesis and Structure of a New Bicadmium (Ⅱ) Complex with Macrocyclic Hexaaza Bearing Hydroxyethyl Pendants

A new bicadmium(??) complex [Cd2L](ClO4)2?1.25H2O (C28H35Cd2Cl4N6O13.25) was synthesized and characterized by X-ray diffraction and ES mass spectral analyses. It crystallizes in the triclinic system, space group P1 with a = 15.630(3), b = 15.990(3), c = 16.330(3) ?, α = 89.90(3), β = 68.87(3), γ = 87.94(3)o, V = 3804.1(13) ?3, Mr = 1034.22, Z = 4, F(000) = 2060, Dc = 1.806 g/cm3, T = 293(2) K, μ = 1.468 mm-1 and λ = 0.71073 ?. The structure was refined to R = 0.0779 and wR = 0.1960 for 7034 observed reflections with I > 2σ(I).

Organic Electrofluorescent Materials Using Pyridine-Containing Macrocyclic Compounds

Novel pyridine-containing macrocyclic compounds, such as 6,12,19,25-tetramethyl-7,11,20,24-dinitrilo-dibenzo [b,m]1,4,12,15-tetra-azacyclodoc osine （TMCD）, were synthesized and used as electron transport layer in organic electroluminescent devices. Devices with a structure of glass/indium-tin oxide/arylamine derivative/ tris（quinolinolato）aluminum（Ⅲ） （Alq）/TMCD/LiF/Al exhibited green emission from the Alq layer with external quantum efficiency of 0.84% and luminous efficiency of 1.3 lm/W. The derivatives of TMCD were synthesized and characterized as well. These compounds were also found to be useful as the electron-transporting materials in organic electroluminescent devices.

A New Macrocyclic Trichochecene from Soil Fungus

From fermentation broth of soil fungus 254-2 obtained from Yunnan province, a new macrocylic trichochecene was isolated. The structure was determined on the basis of spectroscopic evidences especially the 2-D NMR spectra.

Synthesis and Crystal Structure of a New Dinuclear Manganese(Ⅱ) Manganese(Ⅲ) Complex of a Macrocyclic Ligand

A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P2 1/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ 2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N 3O 3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.

Syntheses and Structures of Three Hybrid Materials Using Vanadium Polyoxoanions and Macrocyclic Copper Complex as Building Blocks

The reactions of the four-coordinated macrocyclic copper complex [CuL]（ClO4）2（L = 1,4,8,11-tetraazacyclotetradecane） with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO3]2·2.33H2O（1）, [CuL]3[V（10）O（28）]·8H2O（2） and [Cu L]3[V6O（18）]·8H2O（3）. Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V6O（18）]6- ring, [V（10）O（28）]6- cluster, and [V（12）O（35）]^10- ring, were isolated from the same reactant NH4VO3 under different conditions. The [CuL]^2＋ bridges the [V10O28]6- clusters to form a two-dimensional sheet in 2, and link the [V6O（18）]^6- rings in 1 and [V（12）O（35）]^10- rings in 3 into three-dimensional frameworks, respectively.

NEW MACROCYCLIC COMPOUND,CLEMOCHINENOSIDE B FROM CLEMATIS CHINENSIS

The structure of a new macrocyclic compound,clemochinenoside B, isolated from the root of Clematis chinensis was elucidated by means of NMR,FAB-MS,NOE and chemical hydrolysis.

The Synthesis of Podophyllotoxin Derivatives with Macrocyclic Dilactone

Starting from podophyllotoxin, five new derivatives with macrocyclic dilactone 5 similar to 9 have been synthesized,and their structures were confirmed by IR, MS,H-1 NMR as well as HRMS. The key step is cyclization by high dilution method.