Nucleophilic substitution of hydrogen (3-H) in quinoxalone by arylamines

When quinoxalone is heated with aromatic amines in acetic acid in the presence of ammonium nitrate, a hydrogen undergoes nucleophilic substitution to give the corresponding 3-(4′-aminophenyl)quinoxalones.     

One-pot synthesis of aromatic homoallylic alcohols from aldehydes and Grignard reagents promoted by Titanium(IV) tetraisopropanolate

An efficient method of Titanium(IV) mediated one-pot reaction approaching aromatic homoallylic alcohols from aldehydes and dual Grignard reagents was developed with good isolated yields. This method could use aromatic-, heteroaromatic-, or aliphatic-aldehydes as starting materials. However, electron-riched benzaldehyde or cinnamaldehyde tended to precede further hydroxyl eliminations to give all conjugated structures as demonstrated.     

Kinetics and mechanism of osmium(VIII) catalyzed oxidation of tellurium(IV) by cerium(IV)

The reaction is first order in substrate and catalyst and zero order in cerium(IV). The rate decreases with increasing [H⁺] as well as with increasing ionic strength. H and S have been found to be 44.8 kJ mol^–1 and 161.8 JK^–1 mol^–1 respectively. A mechanism is proposed.

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(IV). [H⁺], . , H S 44,8 ·^–1 161,8 ·^–1–1, . .

     

Polarographic determination of osmium with the osmium(VIII)-cerium(IV)-arsenic(III) system

A highly sensitive and novel polarographic method has been developed for determination of ultratrace amounts of osmium, based on the catalysis of the cerium(IV)-arsenic(III) reaction by osmium(VIII). The reaction rate is monitored by measuring the arsenic(III) with a single-sweep oscillopolarograph. Osmium concentrations from 7.0 x 10(-11) to 5.0 x 10(-9)M can be determined by the initial rate method. The method has been applied to determination of osmium in refined ore and chlorination residues with satisfactory results.     

Nucleophilic substitution of hydrogen (9-H) in acridinium salts by phenols

Under oxidative conditions, quaternary and protic acridinium salts undergo substitution of the hydrogen atom in the 9 position by a phenol residue to give 9-hydroxyarylacridines. The latter may be formed under the same conditions from complexes of acridine hydrochloride with phenols obtained by an independent method.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 266–271, February, 1976.     

Nucleophilic substitution by grignard reagents on sulfur mustards

With proper activation of the leaving group, sulfur mustards react with Grignard reagents with neighboring group participation of the sulfur atom. 2,6-Dichloro-9-thiabicyclo[3.3.1]nonane is especially useful in this regard, providing clean reactivity with organomagnesium nucleophiles on a topologically constrained scaffold.     

Steric Effects in Nucleophilic Aromatic Substitution reactions with aromatic amines 12th communication on nucleophilic aromatic substitution reactions

The kinetics of the S_NAr reactions of aniline and N-methylaniline with a variety of substituted nitrochlorobenzenes in acetonitrile demonstrate that the formation of the intermediate σ-complex is rate determining. The ratio of the rate constants of the aniline and the N-methylaniline reactions (k_A/k_M) increases with increasing size of the 6-substituent; with picryl chloride k_A/k_M reaches a value of over 20 000. The reaction of aniline with 4-X-2,6-dinitrochlorobenzenes is subject to considerably larger para-substituent effects than the corresponding reactions with N-methylaniline. These results are interpreted in terms of two effects: (i) A primary steric effect, which renders the approach of N-methylaniline to the substrate difficult. (ii) A shift towards earlier, more reactant-like transition state structures caused by the primary steric effect. In early transition states the activating power of the electron-withdrawing substituents in the substrate is expected to be relatively small. An early transition state for the slow N-methylaniline reaction and a late transition state for the fast aniline reaction is in apparent contradiction to what would be expected on the basis of the Hammond postulate.     

Reactivities of osmium(VIII), iridium(IV) and platinum(IV) towards glycolaldehyde

Oxidations of glycolaldehyde (GA) to glyoxal by osmium(VIII), iridium(IV) and platinum(IV) have been investigated in aqueous solution, and the orders with respect to each [reactant] determined. The reaction involving iridium(IV) takes place through intermediate formation of free radicals in a MeCO₂Na-MeCO₂H buffer medium, whereas a one-step two-electron transfer process occurs in the oxidations by Os^VIII and Pt^IV in an alkaline medium. Mechanisms consistent with the experimental findings are proposed. This revised version was published online in June 2006 with corrections to the Cover Date.     

Rapid and selective determination of osmium(IV) by UV-visible spectrophotometry using o-methylphenyl thiourea as a chromogenic chelating ligand: sequential separation of osmium(IV), rhodium(III) and platinum(IV)

The objective of this research work was to develop a simple, highly sensitive and precise method for spectrophotometric determination of osmium(IV). O-Methylphenyl thiourea (OMPT) coordinates with osmium(IV) as a 1:1 (osmium(IV)–OMPT) complex in hydrochloric acid media (0.8 mol l^?1). The novelty of the investigated method is instant complex formation at room temperature with no need of heating or standing. The complex is stable for more than 8 days. The method is applicable over a wide linearity range (up to 110 µg ml^?1). A low reagent concentration is required (2 ml, 0.009 mol l^?1 in ethanol). The complex exhibits maximum absorption in the range of wavelength 510–522 nm and 514 nm was selected for further study. The molar absorptivity was 1.864 × 10³ l mol^?1 cm^?1, Sandell’s sensitivity was 0.102 µg of osmium(IV) cm^?2. Proposed method was successfully applied for separation and determination of osmium(IV) from binary and ternary synthetic mixtures containing associated metal ions. A scheme for mutual separation of osmium(IV), rhodium(III) and platinum(IV) is developed.     

Nucleophilic substitution of hydrogen in naphthalene by chloride(Cl~-)in ionic liquids

Nucleophilic aromatic substitution of hydrogen in non-activated aromatic ring,a very rare phenomenon in organic chemistry,is found in ionic liquids containing Cl^- as anion under mild reaction conditions.The reaction may be carried out by the addition of the halogen-bonding adduct（Br₂Cl^-） as nucleophile to aromatic ring carbon atom,leading to the formation of the nucleophilic substitution product.