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4?,4? (5?)-Di-tert-butyldibenzo-18-crown-6 (DTBB18C6) was synthesized by improving the electrophilic aromatic substitution of dibenzo-18-crown-6 (DB18C6) using tert-butyl alcohol (TBA) as alkylation reagent, H3PO4 (85 wt%) as catalyst and CH 2Cl2 as solvent. Experimental results show that the optimized reaction conditions were 0.03 mol L-1 for TBA concentration, 2.5 for TBA/DB18C6 molar ratio, 0.006 mol L-1 for H3PO4 concentration, 50 C reaction temperature, and 6 h reaction time. Under the optimum reaction conditions, DTBB18C6 yield can reach 43.65%.

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The spectrophotometric kinetic charge-transfer complex formation of iodine trichloride (ICl3) with Dibenzo-18-crown-6 (DB18C6), Dicyclohexyl-18-crown-6 (DC18C6) has been studied in chloroform; dichloromethane and propylene carbonate solutions at different temperatures. The results indicated immediate formation of an electron donor-electron acceptor complex; which is followed by two relatively slow consecutive reactions. The pseudo-first-order rate constants for the formation of the ionic intermediate and the final product have been evaluated at various temperatures by computer fitting of the absorbance-time data to appropriate equations. The influences of both the crown’s structure and the solvent properties on the formation of donor-electron acceptor complexes and the rates of subsequent reactions are discussed.

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Abstract Directed by potassium-crownether host-guest cation, a unique octameric eicosanuclear heterothiometallic Mo/S/Cu cluster [K(dibenzo-18-crown-6)(DMF)2]4[Mo8S32Cu12] (1) was synthesized by the reaction of (NH4)2MoS4, CuI, KI, dibenzo-18-crown-6 in DMF solution. 1 was characterized by elemental analysis, IR, thermogravimetric analysis, X-ray powder and single crystal diffractions. 1 crystallizes in the tetragonal space group I41cd. The anionic octameric eicosanuclear [Mo8S32Cu12]4- cluster exhibits a supra-cubane-like skeleton, fabricated by four nest-shaped clusters [Mo(mu1-S)(mu3-S)3Cu3]+ and four flywheel-shaped clusters [Mo(mu2-S)3(mu4-S)Cu3]+ linking together through shared Cu atoms. The cation [K(dibenzo-18-crown-6)(DMF)2]+ of 1 exhibits the host-guest configuration, where K+ is embedded in the center of dibenzo-18-crown-6. Furthermore, Z-scan studies (532 nm, 21 ps pulses) reveal that 1 possesses effective third-order nonlinear optical (NLO) properties.

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Chiral Catalysts,
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14187-32-7, Name is Dibenzo-18-crown-6, molecular formula is C20H24O6, belongs to chiral-catalyst compound, is a common compound. In a patnet, once mentioned the new application about 14187-32-7, Product Details of 14187-32-7

Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda3-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph2IBF4 and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction. 1H NMR analyses and CSI-MS spectra showed that, in dichloromethane solution, Ph2IBF4 exclusively forms the 1:1 complex with 18C6 (binding constant Ka, 1.02 x 103 M-1). The binding constants decrease with the increased solvent donor ability (Gutmann’s DN). Changing the heteroatom ligand from BF4 to the less nucleophilic PF6 and AsF6 increased the binding constant by about six times. Substitution of an electron-withdrawing group onto the para position of Ph2IBF4 tends to increase in the complex stability. A linear Hammett relationship (p = 0.59) between log Ka and sigmap+ values of substituents indicates that the diaryl-lambda3-iodanes with electropositive iodine(III) interact more efficiently with 18C6. Decreased binding magnitude was measured with 15C5, dibenzo-18C6, dibenzo-21C7, and dibenzo-30C10.

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The complexation of sulfanilamide with different crown ethers has been studied by 1H NMR, IR and UV?visible spectra in solution state. The interactions of crown ethers with sulfanilamide have been supported by density, viscosity, refractive index indicating higher degree of complexation in case of dicyclohexano-18-crown-6. The complexation stoichiometry was determined by Job plots and the 1:1 stoichiometry is found for all the complexes; the complex formation is confirmed by spectral shifts. The Benesi-Hildebrand method is used to calculate the binding constant of the complexes of sulfanilamide with crown ethers. The Gibbs free energy change of the inclusion complex process is calculated and the process is found to be spontaneous. Hydrogen bonding was observed to be the most important interaction for the complexation and pi?pi interactions also have minor contribution towards complexation of dibenzo-18-crown-6. Various factors that influence the stability of the complexes formed have been discussed for thermodynamic consideration.

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The relationship between the rate of carrier-facilitated transport of metal cations through chloroform membranes containing macrocyclic ligand carriers and the stability constant of the cation-carrier complex in methanol solution was investigated.Several macrocyclic ligand carriers were used in transporting Na+, K+, Rb+, Cs+, Ca2+, Sr2+, and Ba2+.For maximum cation transport, an optimum range in value of the cation-carrier complex stability constant was shown to exist.The rate cation transport decreased rapidly at stability constant values higher or lower than this range.The maximum observed transport occurred for carriers having log KMeOH values from 5.5 to 6.0 for K+ and Rb+ and 6.5 to 7.0 for Ba2+ and Sr2+.For all cations, little or no transport occurred with carriers having log KMeOH less than 3.5 – 4.0.An equation was derived which correctly predicts the observed variation of cation transport rate with log KMeOH over a wide range of log KMeOH values.This equation makes possible the estimation of either log K or cation-transport rate in certain cases if the other of the two values is known.

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Chiral Catalysts,
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Reactions exchanging the cation in (nBu4N)[Ni(dmit)2] to cis-cyclohexane-1,4-diammonium (cis-CHDA) in the presence of [18]crown-6, benzo[18]crown-6 (B[18]crown-6) and dibenzo[18]crown-6 (DB[18]crown-6) yielded crystals of the monovalent [Ni(dmit)2] complex, namely (cis-CHDA)([18]crown-6)2[Ni(dmit)2]2 (1), (cis-CHDA)(B[18]crown-6)2[Ni(dmit)2]2 (2) and (cis-CHDA)(DB[18]crown-6)2[Ni(dmit)2]2 (3). The two ammonium groups (-NH3+) of the cis-CHDA dication at axial and equatorial positions interact with oxygen atoms of the corresponding upper and lower crown ethers to form sandwich-type supramolecular cationic structures. The lateral [Ni(dmit)2]- anion arrangements through S-S contacts along the short and long axis of [Ni(dmit)2] anions were realised in crystals of 1, 2, and 3 by the asymmetrical cis-CHDA dication. The temperature- and frequency-dependent anisotropic dielectric constants of a crystal of 1 were evaluated along the a, b and c axes, where the thermally activated motion of the structurally flexible cis-CHDA dication was consistent with the dielectric responses. The motions, dielectric properties and magnetism of [Ni(dmit)2]- salts with flexible cis-cyclohexane-1,4-diammonium ion have been investigated. Copyright

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Reference:
Chiral Catalysts,
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Catalytic Friedel-Crafts acylation of benzene and unactivated benzenes such as chlorobenzene and nitrobenzene have been successfully carried out using activated hematite (alpha-Fe2O3) as a new, heterogeneous and green catalyst. Sonication of neat alpha-Fe2O3 in a water bath under air atmosphere at room temperature followed by heating at 200C, dramatically increase the activity of alpha-Fe2O 3. With the catalyst loading as low as 5.0mol%, a wide variety of benzene derivatives were easily converted into the corresponding acylated products in a clean and high-yielding acylation reaction. It was found that the activated alpha-Fe2O3 could be efficiently recycled and reused several times by simple washing with ethyl acetate, this cannot be attained with most of the traditional catalysts. Copyright

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Reference:
Chiral Catalysts,
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The equilibrium constant of extraction of lithium, sodium, or potassium picrates, MPi, with 18-crown-6 or dibenzo-18-crown-6 between water and dichloromethane was determined spectrophotometrically and compared with literature values. In all instances, a 1:1:1 complex was extracted. The value of the ionic association constant of the complexed potassium picrate in the organic phase agrees well with that from electrolytic conductivity data. The latter reveals the presence of both cationic and anionic ion triplets in solutions >3 × 10-3 mol-1 dm-3. The effect of temperature on the solubility of dibenzo-18-crown-6 in water saturated with dichloromethane yields DeltaH = -16.4 kJ mol-1 and DeltaS = -36.02 kJ mol-1 K-1. Values of the activity coefficient of dibenzo-18-crown-6 at 296.1 K (“salting out effect”) in aqueous lithium chloride (0.10 to 0.25 mol dm-3) were estimated from the effect of the salt on the solubility, while the activity coefficient of the crown ether in dichlaromethane saturated with water was evaluated from the effect of the salt on the partition coefficient. An estimate of the activity coefficient product, y(K+)y(Pi-), in the aqueous lithium chloride solutions was made from the effect of this electrolyte on the extraction constant.

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Chiral Catalysts,
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Five metal complexes of 2-methylisothiazol-3(2H)-one (MIO), [Co III(NH3)5(MIO)]3+, [Ru II(NH3)5(MIO)]2+, [Ru III(NH3)5(MIO)]3+, [Pt IICl3(MIO)]-, and trans-[UVIO 2(NO3)2(MIO)2], were synthesized, and their structures were determined by single-crystal X-ray crystallography. MIO is an ambidentate ligand and coordinates to metal centers through its oxygen atom in the cobalt(III), ruthenium(III), and uranium(VI) complexes and through its sulfur atom in the ruthenium(II) and platinum(III) complexes. This result suggests that MIO shows preferential behavior on its donating atoms. We also studied the electron-donor abilities of the oxygen and sulfur atoms of MIO. Various physical measurements on the conjugate acid of MIO and the MIO complexes allowed us to determine an acid dissociation constant (pKa) and donor number (DN) for the oxygen atom of MIO and Lever’s electrochemical parameter (EL) and a relative covalency parameter (kL) for the sulfur atom.

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