The reaction of 2-methoxy-3-nitrothiophene with N-benzylmethylamine in methanol

1990

The kinetics of the title reaction has been studied in methanol as a function of amine and methoxide ion concentrations. The kinetic coefficients obtained point out that the reaction is catalysed by methoxide through a SB catalysis mechanism.

Crystal structure and reactivity of 2-chloro-3,5-dinitrothiophene and of 2-phenylsulphonyl-3,5-dinitrothiophene with nucleophiles

1988

The geometry obtained by a crystal structure determination of the title compounds, as compared with that of the analogous benzene derivatives, along with results of ab initio calculations, is used to interpret the different SNAr reactivities in some thiophene and benzene compounds. The smaller rotation of the nitro groups with respect to the aromatic rings observed in thiophene derivatives should be considered a relevant factor in the higher reactivity in the thiophene series.

On the Nucleophilic Reactivity of 4,6-Dichloro-5-nitrobenzofuroxan with Some Aliphatic and Aromatic Amines: Selective nucleophilic substitution

2020

The reaction rates for the nucleophilic aromatic substitution of 4,6-dichloro-5-nitrobenzofuroxan 1 with eight aliphatic amines (characterized by very different basicities/ nucleophilicities) and three anilines have been measured in both methanol and toluene. The obtained rates have been related to the basicity (pKaH in water and Kb in benzene) or nucleophilicity (N Mayr constants) of the tested amines. The whole of the obtained kinetic data has furnished useful information on the high nucleophilic reactivity of benzofuroxan derivatives, which has been related essentially to two factors: the high electron-drawing ability/power of the condensed furoxan ring and the low aromatic character of …

Mononuclear heterocyclic rearrangements 5. Kinetic Investigation of the behaviour of (e)- and (z)-phenylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadia…

1980

The kinetic behaviour of the geometrical isomers I-E and I-Z of the title compound in the presence of piperidine in benzene has been investigated. The kinetic results suggest that I-Z rearranges directly into 2,5-diphenyl-4-benzoylamino-1,2,3-triazole (II), whereas I-E probably rearranges only through the intermediate I-Z formed by isomerization. All the reactions studied are piperidine-catalyzed.

Mononuclear heterocyclic rearrangement. Part 6 . Studies on base catalysis of the rearrangement of the (Z)-p-nitrophenylhydrazone of 3-benzoyl-5-phen…

1981

Linear free energyortho-correlations in the thiophene series. Part IX . Kinetics of esterification with diazodiphenylmethane of some 3-, 4-, and 5-su…

1981

The rate constants for the esterification of some 3-, 4-, and 5-substituted thiophene-2-carboxylic acids with diazodiphenylmethane in methanol at 25° have been measured. The reactivity of some para- and ortho-substituted benzoic acids has also been determined. Logarithmic kinetic constants for ortho-, meta-, and para-like substituted thiophene-2-carboxylic acids furnish an excellent linear free energy relationship when plotted versus Δpka (β 0.89, r 0.989, C.L. > 99.9%, n 18, i 0.04), thus confirming the peculiar behaviour of five-membered ring derivatives. The correlation with σH values offers an additional proof of the hyper-ortho character of the 2,3-relation in thiophene derivatives. pa…