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KINETICS AND MECHANISM OF MONOMOLECULAR HETEROLYSIS OF FRAMEWORK COMPOUNDS. II. IONIZATION OF 1-ADAMANTYL IODIDE IN ACETONITRILE

The heterolysis of 1-adamantyl iodide in acetonitrile was studied preparatively and kinetically (in the presence of triphenylverdazyl as internal indicator).Additions of LiClO4, Et4N+ClO4-, Et4N+OTs-, Et4N+I-, and Et4N+Br- do not affect the reaction rate; the normal salt effect and the salt effect of the law of mass action do not appear.Additions of water increase the reaction rate a little, while additions of LiBr, Bu4N+NO3-, LiCl, and Et4N+Cl- reduce it greatly.It is suggested that an intimate ion pair of the substrate is converted into a solvent- separated ion pair in the controlling stage of the reaction.

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Chiral Catalysts,
Chiral catalysts – SlideShare

 

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PREPARATION OF CHLOROMETHYL DERIVATIVES OF DIBENZO-18-CROWN-6 AND SYNTHESES BASED ON THEM

The reaction of chloromethylated dibenzo-18-crown-6 and some monosubstituted derivatives (4′-acetyl-, 4′-propionyl-, and 4′-tert-butyldibenzo-18-crown-6) was studied.Modification of the chloromethyl group resulted in the synthesis of various dibenzo-18-crown-6 derivatives.

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Chiral Catalysts,
Chiral catalysts – SlideShare

 

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Children learn through play, and they learn more than adults might expect. Science experiments are a great way to spark their curiosity, get their minds active, and encourage them to do something that doesn¡¯t involve a screen. 39648-67-4, C20H13O4P. A document type is Article, introducing its new discovery., Quality Control of: (R)-4-Hydroxydinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide

In situ generation of dihydropyridine for the enantioselective transfer hydrogenation of 1,4-benzoxazines

A new strategy for the enantioselective transfer hydrogenation of benzoxazines involving an in situ generation of Hantzsch ester has been developed. Dihydroadducts were isolated in good yields (75-99%) and enantioselectivities (89-96% ee).

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Chiral Catalysts,
Chiral catalysts – SlideShare

 

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.14187-32-7, Name is Dibenzo-18-crown-6, molecular formula is C20H24O6. In a Article£¬once mentioned of 14187-32-7, SDS of cas: 14187-32-7

Thirteen cationic ionophores: Their acute toxicity, neurobehavioral and membrane effects

Thirteen cationic ionophores (12-Crown-4, 15-Crown-5, 18-Crown-6, Dibenzo 18-Crown-6, Dicyclohexano 18-Crown-6, 24-Crown-8, Dicyclohexano 24-Crown-8, Lasalocid, Hexacyclen trisulfate, Chiral binapthol, Valinomycin, Monensin, and A-23187) were evaluated for acute toxicologic properties, including lethality and neurobehavioral effects in multiple species (rats, rabbits, and mice) by multiple routes, skin and eye irritation and effects on membrane permeability to physiologic cations. Attention was focused on determining minimum neurobehavioral effect levels and characterizing the spectrum of these effects at different dose levels. While LD50’s followed one pattern, this was not the case with other effects. Cluster and factor analysis suggest that, though the primary mechanism of action is alteration of membrane permeability to specifi-cations (qualitative types of activity correlate with the results of membrane permeability studies), which ions are provided an increased passage varies with ring size and charge dispersion. In the intact animal absorption markedly modifies these results.

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Chiral Catalysts,
Chiral catalysts – SlideShare

 

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Catalytic asymmetric chemodivergent arylative dearomatization of tryptophols

The first catalytic asymmetric arylative dearomatization of tryptophols has been established. By using quinone imine ketals as aryl group surrogates and modulating the reaction conditions, the cascade reaction of tryptophols with quinone imine ketals in the presence of chiral phosphoric acid afforded two series of arylative dearomatization products with generally high yields (up to 99%), and excellent diastereo- and enantioselectivities (all > 95 : 5 dr, 90% to 99% ee) in a chemoselective manner.

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Chiral Catalysts,
Chiral catalysts – SlideShare

 

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Reference of 14871-92-2, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.14871-92-2, Name is (2,2¡ä-Bipyridine)dichloropalladium(II), molecular formula is C10H8Cl2N2Pd. In a article£¬once mentioned of 14871-92-2

The synthesis and characterization of 10 complexes, [Pd(bipy)(R-TU) 2]Cl2 and [Pd(phen)(R-TU)2]Cl2 (bipy = 2,2?-bipyridyl; phen = 1,10-phenanthroline; R-TU = N-alkyl substituted thioureas), is presented. The conformational and dynamic behavior in solution, analyzed by several NMR techniques, is compared to that of the free thiourea ligands. Spectra at variable temperatures of the free thioureas are consistent with hampered rotation around the C-N bonds. Mono-alkyl derivatives, in methanol, show equilibria between syn and anti conformers, whereas di-alkyl thioureas show equilibria between the syn-anti and syn-syn conformers (syn and anti indicate the position of the alkyl chain with respect to the S atom over the two amino-branches). Syn protons of the alkyl-chains are converted into the corresponding anti protons by C-N rotation, which also exchanges external (close to the S atom) to internal N-H (on the opposite side with respect to the S atom) within the NMR timescale. This is also observed for the corresponding PdII complexes, which, according to the enhancement of the double C-N bond character, present slower syn/anti exchanges. Moreover, metal coordination selects anti conformers for the mono-alkyl thioureas, and syn-anti conformers for the di-alkyl thioureas.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

 

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A true biphasic [aqueous-organic] system for the coupling of water soluble sodium acrylate with different aryl halides for the synthesis of cinnamic acid derivatives has been developed, employing palladium catalysts that is soluble in organic phase. Amongst them, palladacycle was found to be stable in presence of water and could be recycled for four times with no loss in the activity. Such a system facilitates easy recycle of catalyst and also the removal of the salts from the catalyst phase, ensuring high activity with respect to cumulative turn over number (TON) and turn over frequency (TOF). The reaction was facilitated by organic as well as inorganic bases. The efficiency of the catalyst, role of organic/inorganic bases on the activity is reported.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

 

Top Picks: new discover of Bis(benzonitrile)palladium chloride

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Reference of 14220-64-5, The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.14220-64-5, Name is Bis(benzonitrile)palladium chloride, molecular formula is C14H10Cl2N2Pd. In a Article£¬once mentioned of 14220-64-5

New mixed-ligand picrate complexes of cobalt(II), formed by interaction of cobalt(II) picrate with 2-aminobenzothiazole (ABZT), 2-(2′- aminophenyl)benzothiazole (2′-AMPHBZT), 2-(3′-aminophenyl)benzothiazole(3′- AMPHBZT), bipyridyl(Bipy), o-phenonthroline (Phen), and 2,6- bis(benzimidazole-2’yl)pyridine(BBZLY) are described. The complexes have been characterised by elemental analyses, molar conductances, magnetic and decomposition temperature measurements, electron spin resonance, infrared and electronic spectral studies. They have the composition [Co(PA)2(L-L)2], where L – L= ABZT, 2′-AMPHBZT, 3’AMPHBZT, Bipy, Phen or BBZLY. A trans octahedral structure has been tentatively proposed for these complexes.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

 

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UO2Cl4.

During the course of our structural investigations of f-element-crown ether complexes, we have had the opportunity to study several uranyl compounds. The title compound was prepared by the direct reaction of UCl//4 with dibenzo-18-crown-6 in a 1:3 ratio of CH//3CN and CH//3OH and recrystallized from pentane. The partial oxidation product left bracket UO//2Cl//4 right bracket left bracket (OH)//3) (dibenzo-18-crown-6) right bracket //2 multiplied by (times) CH//3OH, crystallizes in the orthorhombic space group Fddd. There are eight formula units in the unit cell. The uranyltetrachloride dianion is octahedral and the oxonium ion is hydrogen bonded to the crown ether. Two dibenzo-18-crown-6 moieties envelope the solvent molecule.

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Chiral Catalysts,
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Uranium(IV) terminal hydrosulfido and sulfido complexes: Insights into the nature of the uranium-sulfur bond

Herein, we report the synthesis and characterization of a series of terminal uranium(iv) hydrosulfido and sulfido complexes, supported by the hexadentate, tacn-based ligand framework (Ad,MeArO)3tacn3- (= trianion of 1,4,7-tris(3-(1-adamantyl)-5-methyl-2-hydroxybenzyl)-1,4,7-triazacyclononane). The hydrosulfido complex [((Ad,MeArO)3tacn)U-SH] (2) is obtained from the reaction of H2S with the uranium(iii) starting material [((Ad,MeArO)3tacn)U] (1) in THF. Subsequent deprotonation with potassium bis(trimethylsilyl)amide yields the mononuclear uranium(iv) sulfido species in good yields. With the aid of dibenzo-18-crown-6 and 2.2.2-cryptand, it was possible to isolate a terminal sulfido species, capped by the potassium counter ion, and a “free” terminal sulfido species with a well separated cation/anion pair. Spectroscopic and computational analyses provided insights into the nature of the uranium-sulfur bond in these complexes.

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Chiral Catalysts,
Chiral catalysts – SlideShare