Synthesis and Crystal Structure of 7,7-Dimethyl-2-amino-3-cyano-4-(3,4-methylenedioxylphenyl)-5-oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran

The title compound 7,7-dimethyl-2-amino-3-cyano-4-(3,4-methylene- dioxylphenyl)-5-oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran(C19H18N2O4, Mr=338.35) is mono- clinic, space group C2/c with a=26.753(5), b=9.409(2), c=16.036(3)? b=121.00(1), Z=8, V=3460(1)?, Dc=1.299g/cm3, m (MoKa)=0.092mm-1, F(000)=1424, R=0.0410 and wR=0.0926 for 3138 observed reflections (I >2s (I)). X-ray analysis reveals that atoms C(8), C(9), C(10), O(3), C(12) and C(13) form a six-membered ring in which the distances of C(9)-C(10) and C(12)-C(13) are 1.342(2) and 1.331(2) ? respectively, which show that they are C=C double bonds. In addition, there is hydrogen bond in the product molecule.

Synthesis and Crystal Structure of Methyl(7,7-Dimethyl-2-amino-4-(4-chlorophenyl)-5-oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran-3-yl)Carboxylate

The title compound methyl (7,7-dimemyl-2-amino-4-(4-chlorophenyl)-5-oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran-3-yl) carboxylate (C19H20ClNO4, Mr = 361.81) was synthesized and crystallized. The crystal belongs to triclinic, space group P 1 with a = 8.519(2), b = 10.346(2), c = 11.481(3) A, α = 108.16(1), β = 107.78(2), γ= 91.83(2)°, Z = 2, V = 906.5(3) A3, Dc = 1.326 g/cm3, μ(MoKα) = 0.234 mm-1, F(000) = 380, R = 0.0467 and wR = 0.1270 for 3142 observed reflections (I > 2σ(I)). X-ray analysis reveals that the C(7), C(8), C(9), O(1), C(10) and C(11) atoms form a six-membered ring which adopts a boat conformation. In the ring, the distances of C(8)-C(9) and C(10)-C(11) are 1.332(3) and 1.357(3) A, respectively, which indicates that they are C=C double bonds. Another six-membered ring (C(8)-C(9)-C(15)-C(14)-C(13)-C(12)) adopts the half-chair confonnation. In addition, there are intermolecular hydrogen bonds in the crystal structure.

The Novel Benzo-15-Crown-5 with Palladium(II) Complex: [Na(B15CS)]_2,[Pd(SCN)_4]

A novel Pd(II) Benzo-15-crown-5 complex [Na(B15CS)]_2[Pd(SCN)_4] has been isolated and characterized by IR and X-ray diffraction analysis. The crystal structure belongs to monoclinic, space group P2_1,/n with cell dimensions, a = l.0164(6), b = l.3743(3), c = l.4987(7) nm, β = 95.248(6) °, V = 2.0847 'nm_3, Z = 2, F(000) = 944, R = 0.053, Rw = 0.072. The compound consists of two [Na(B15CS)]+ complex canons and a [Pd(SCN)4_]^(2-) complex anion. Each sodium ion is coordinated by five crown ether oxygen atoms and one N atom from the SCN group of [Pd(SCN)_4]^(2-) to form stable neutral complex.

Dioxygen affinities and catalytic oxidation performance of cobalt(Ⅱ) hydroxamates with benzo-15-crown-5 pendants

The oxygenation constants （Ko2） of cobalt（Ⅱ） hydroxamates （CoL^1 2-CoL^3 2） with benzo-15-crown-5 （B15C5） pendants were measured over the range of -5 to ＋20 ℃, and the values of thermodynamic parameters （ΔH^0 and ΔS^0） were calculated based on these （Ko2） values, Meanwhile, these crowned complexes were employed to the oxidation for p-xylene to p-toluic acid with air at 110Δ under normal atmospheric pressure. The effects of B15C5 pendant and the length of chain bonded to B15C5 in these complexes on the O2-binding capabilities and oxidation for p-xylene were investigated with the comparison of crown-free analogues CoL^4 2.

Molecular Design of Crown Ethers. 19~1. Synthesis of Novel Disulfide and Diselenide-Bridged Bis (benzo-12-crown-4)s and their Ag^+ Selective Electrode Properties

Two novel heteroatom-bridged his (benzo-12-crown-4 ether)s, i.e. his [2-nitro-4,5 (1,4,7,10-tetraoxadecamethylene) disulfide 1 and diselenide 2, have been synthesized. X ray crystallographic structure was obtained for 1. Ion selective electrodes (ISE) for Ag+, containing 1 and 2 in PVC membrane as neutral carriers, were prepared, and their selectivity coefficients for Ag^+ (K_(Ag.M)^(pot)) were determined against other heavy metal ions, alkali and alkaline-earth metal ions. and ammonium ion. These ISEs showed excellent Ag^+ selectivities, log K_(Ag.M)^(pot) ≤ -3.8, against most of the interfering canons examined, except for Hg^+.

Michael Addition Reaction without Catalyst: The Synthesis of 2-Amino-5, 6, 7, 8-tetrahydro-5-oxo-4-aryl-7, 7-dimethyl- 4H-benzo-[b]-pyran Derivatives

A series of tetrahydrobenzo-[b]-pyran derivative was synthesized by the reaction of arylmethylene malononitrile or arylmethylene cyanoacetate with dimedone in ethylene glycol at 80C without catalyst. The structures of the two products were characterized by X-ray diffraction.

STUDIES ON HETERO-MACROCYCLIC POLYETHER(1).THE SYNTHESIS OF 10-SELENA BENZO-15-CROWN-5

The synthesis of a new type of hetero-macrocyclic polyether 2,3-henzo-1,4,7,13-tetraoxa-10-selenacyclopentadeca-2-ene is deseribed.

Simple Detection Method of Biogenic Amines in Decomposed Fish by Intramolecular Excimer Fluorescence

Biogenic amines are known to have various biological functions such as not only neurotransmitter and cell proliferation but also food poisoning. Bacterially-decomposed amines such as histamine, agmatine, putrescine, cadaverine, spermidine and spermine cause allergic symptoms. We developed simple method for measurement of polyamine as indicator of food decomposition with a fluorometer by using 4-(1-Pyrene)butyric acid N-hydroxysuccinimide ester (PSE). PSE reacts with primary and secondary amino moieties of polyamines and produces the intramolecular excimer fluorescence. Excimer fluorescence with broad peak at around 470 nm was clearly detected in linear type biogenic amines such as putrescine, cadaverine, spermidine and spermine at 10 mM. However neither histamine nor trimethylamine altered the fluorescence. Decomposed sardine and mackerel by improper storage showed stronger intensity than fresh ones. Comparing with OPA-method, PSE method was useful for screening biogenic amines present in food, esp. fish since the analysis was simple after one-step purification procedure. An inexpensive system which can rapidly detect biogenic amines from food is necessary in a medium and small-sized food business. The technique using excimer has potential to realize the high through-put screening system for evaluation of food freshness and is expected to bring the public interests such as food security and safety of consumer.

The First Three-dimensional Crown Ether Complex:{[Na(B18-C-6)]_(6)[Pt(SCN)_(6)]}[Pt(SCN)_(6)](SCN)_(2)with Covalent Bond

The novel benzo-18-crown-6(B18-C-6)complex;{[Na(Bl8-C-6)]_(6)[Pt(SCN)_(6)]}[Pt(SCN)_(6)](SCN)_(2)(1)was synthesized and characterized by elemental analysis,IR spectrum and x-ray diffraction analysis.Thr crystal structure belongs to rhomobohedral,space group R-3 with cell dimesions:a=6=1.9933(3),c=2.9760(6)nm,α=β=90,γ=120°,V=10.240(3)nm^(3),Z=3,A,aclcd=1.564 g/cm^(3),F(000)=4908.1 is composed of one{[Na(B18-C-6)]_(6)[Pt(SCN)_(6)]}4+complex cation,one[Pt(SCN)_(6)]^(2-)complex anion and two SCN~anions.{[Na(B18-C-6)]_(6)[Pt(SCN)_(6)3}4+complex cation shows a three-dimensional network structure bridged by Na-O interactions between adjacent[Na(B18-C-6)]+units.The function of[Pt(SCN)_(6)]^(2-)complex anion and two SCN'anions are balancing charge in crystal.

Preparation of a fixed-tetraphenylethylene motif bridged ditopic benzo-21-crown-7 and its application for constructing AIE supramolecular polymers

Benzo-21-crown-7(B21 C7)is one of the most important crown ethers,which not only shows excellent physicochemical properties but also exhibits promising binding capability with dialkylammonium salts.In this paper,we designed and synthesized a fixed-tetraphenylethylene(FTPE)motif bridged ditopic benzo-21-crown-7 molecule(H).The fixed tetraphenylethylene motif endows H with aggregation induced emission(AIE)prope rty.In the presence of a ditopic dialkylammonium salt guest molecule(G),a fluorescent supramolecular polymer with golden luminescent property could be fabricated.This B21 C7-based host-guest supramolecular polymer with golden fluorescence may have potential application in dynamic luminescent materials.

Synthesis of Unsymmetrical Bissalicylaldimine Ligands and bis-Schiff Base Cobalt Complexes with Benzo-10-aza-15-crown-5 Pendant

Novel unsymmetrical bissalicylaldimine bis-Schiff bases with a benzo-10-aza-15-crown-5 pendant and their cobalt complexes have been synthesized via condensation of 3 or 5-[（benzo-10-aza-15-crown-5）-10-ylmethyl] salicylaldehyde with the half unit Schiff bases and characterized by ^1H NMR, IR, mass spectroscopy, elemental analysis, molar conductances and molar magnetic susceptibility.

ESR study on some copper(Ⅱ)complexes of bis(4'-benzo-15-crown-5)

ESR measurements have been carried out for some copper(Ⅱ) complexes of bis(4'-ben- zo-15-crown-5) at 77 K.The results of ESR spectrometric titration indicated that the binuclear com- plexes were prepared in the present system.The binuclear complexes revealed characteristic ESR g-anisotropies (gZ<gX,gY) which are typical of the copper(Ⅱ) complexes with a 3d_Z^2 ground state doublet.However,in this case,the innermolecular copper(Ⅱ)-copper(Ⅱ) spin interaction was not observed.ESR measurements also showed that a small amount of the sandwich type copper(Ⅱ) com- plexes were formed in the presence of excess bis (4'-benzo-15-crown-5).A reasonable explanation was given for the ESR results.

Design, Synthesis and Properties of Novel C60-Crown Dyads by 1,3-Dipolar Cycloaddition

Based on the 1,3-dipolar cycloaddition of azomethine ylide generated in situ from aldehyde and sarcosine attached to C60,two novel benzo-15-crown-5/C60 dyads with a different linking chain in each were designed and synthesized in yields of 30％ and 38％,respectively.It was found that their UV-Vis absorption spectra could be regulated hypsochromically by metal ions complexed.The long and soft linking chain was favorable for cooperate interaction of crown ether unit and C60 unit.

p-Nitrophenyl Picolinate Cleavage by Unsymmetrical Bis-Schiff Base Manganese（Ⅲ） and Cobalt（Ⅱ） Complexes with Aza-Crown Ether or Morpholino Pendants

The unsymmetrical bis-Schiff base manganese（III） and cobalt（II） complexes with either benzo-10-aza-crown ether pendants （MnL1Cl, MnLZCl） or morpholino pendant （MnL3Cl, CoL3） have been employed as models for hy- drolase by studying the kinetics of their hydrolysis reactions with p-nitrophenyl picolinate （PNPP）. A kinetic model of PNPP cleavage catalyzed by these complexes is proposed. The effects of complex structures and reaction temperature on the rate of PNPP hydrolysis have been examined. All four complexes exhibit high catalytic activity and the rate increases with pH under 25℃. The complexes of ligands containing a crown ether group exhibit higher catalytic activities than the non-crown analogues. The catalytic activity of the complexes follows the order Mn（III） 〉 Co（II） under the same ligands.

Cobalt(II) Salen Complex with Two Aza-crown Pendants and Its Analogues as Synthetic Oxygen Carriers

Salen with two aza-crown ether pendants H2L1 and its analogues H2L2--H2L4 were successfully synthesized starting from benzo-10-aza-15-crown-5 (BN15C5) or morpholine. Their structures were characterized by IR, MS, H-1 NMR and elemental analysis, and were confirmed by X-ray diffraction analysis of H2L1. Moreover, the saturated oxygen uptake of their cobalt(II) complexes CoL1-CoL4 in diethyleneglycol dimethyl ether was determined at different temperature. The oxygenation contants ( K-O2) and thermodynamic parameters (DeltaHdegrees and DeltaSdegrees) were calculated. The modulation of O-2-binding capabilities by pendant substituents were investigated as compared with the parent Schiff base complex CoL5 (CoSalen). The results indicate that the dioxygen affinities of CoL have been much more enhanced by aza-crown pendants than that by morpholino pendants, and the O-2-binding capabilities of CoL1 and CoL2 with aza-crown pendants would also be enhanced by adding alkali metal cations.