JOURNAL of the Tunisian Chemical Society

serving the Research, the Education and the Industry

Cycloaddition des N-phényl-C-arylnitrilimines sur des dérivés de la 2-benzylidènebenzo[b]tiophèn-3(2H)-one (thioaurones)

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1,3 dipolar cycloaddition of N-phenyl-C-arylnitrilimines with 2-arylidenebenzo[b]thiophen-3-ones, leads to the formation of pyrazoles after opening of the thiophenonic ring followed by a nucleophile substitution with a second molecule of N-phenyl-C-arylnitrilimine with high yield.

A. Boughaleb, G. Al Houari, B. Bennani, M. Daoudi, B. Garrigues, A. Kerbal, M.El Yazidi

1,3 dipolar cycloaddition, 2-arylidenebenzo[b]thiophen-3-ones, N-phenyl-C-arylnitrilimines, thioaurones, pyrazoles

Pages 109-115

Synthèse de nouveaux dérivés de 2,4-diamino-6-phényl-1,3,5-triazines

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The reactivity of 2,4-diamino-6-phenyl-1,3,5-triazine 1a and 2,4-diamino-6-[4-bromophenyl]-1,3,5-triazine 1b has been studied by the reaction of these substrates on some electrophiles such as acid chlorides, iso- and thioisocyanates and orthoacetate to access diamidotriazines 2, thioureas 3 and imidates 4.

I. Ouerfelli, R. Gatri, M.L. Efrit, J.L. Fillaut

2,4-Diamino-1,3,5-triazine, acyl chloride, isocyanate, thioisocyanate

Pages 117-122

Synthèse et caractérisation de quelques diaminopyrazoles

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The synthesis of series of 3,5-diaminopyrazole derivatives is presented. Isothiocyanates with benzylcyanid derivatives in the presence of base give the mixture of cyanothioacetamides and enthiols. The cyanothioacetamides reacted with hydrazine or methylhydrazine to produce the 3,5-diaminopyrazoles with a good yield. The mechanism was discussed and the structure of all compounds was determined by IR and NMR Spectroscopy (13C, 1H).

S. Manai, M. Boukraa, M.L. Efrit, A. Ben Akacha

Arylacetonitrile, isothiocyanate, hydrazine, methylhydrazine, 3,5-diaminopyrazole

Pages 123-128

Seasonal variation of fatty acids in muscles of tunisian swordfish (Xiphias gladius L.1758)

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The objective of this study is to determine the seasonal variation of the total fatty acids (TFA) level and fatty acids (FA) in white and red muscles of Tunisian swordfish (Xiphias gladius). There is a seasonal variation (p<0.05) of total fatty acids (TFA) and fatty acids both in white and red muscles, with a peak in spring (33.7 ±7.2 %) and summer (26.8±3.2 %). In D1, the seasonal variation of polyinsaturated fatty acids (PUFA) is higher than that of the saturated fatty acids (SFA) and monounsaturated fatty acids (MUFA). Palmitic acid (C16 :0) prevails in the SFA (58.2- 64.3 % of the total SFA), disregarding the season, oleic acid (C18 : 1n-9) is the main MUFA component (56.5 % - 68.1 %), whereas linoleic acid (C18 :2n-6) (0.7 ± 0.3 % - 9.2 ± 4.2 %), eicosapentaenoic acid EPA (C20 : 5n-3) (2.6 ± 0.3 % - 3.5 ± 1.1 %) and docosahexaenoic acid DHA (C22 : 6n-3) (19.2 ± 2.6% - 29.2 ± 1.8 %), are the most important in the PUFA series. Compared to the percentage of (n-6) series fatty acids contained in the TFA of swordfish, the part of the (n-3) series is more important, yielding n-3/n-6 ratios of respectively 6.8, 6.9, 4.1 and 6.7 in autumn, winter, spring and summer. (n-3) and (n-6) fatty acids contained in white muscle of swordfish undergo significant seasonal variations.

M.A. Ben Smida, B. Marzouk, M. El Cafsi

Total fatty acids, poly-unsaturated fatty acids (n-3), poly-unsaturated fatty acids (n-6), eicosapentaenoic acid, docosahexaenoic acid, white muscle, red muscle, swordfish

Pages 129-137

Adsorption de COV par un matériau argileux tunisien organo-modifié

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Leaching of industrial waste storage settings and the release of the organic vapor can lead to severe pollution of the water resources and atmosphere. Geomaterial barriers made from cement, bentonite and active carbon can overcome such problems. The first part of this work deals with preparation of new adsorbents able to contend against the pollutant gas outburst of the type Volatile Organic Compounds (VOCs). These geomaterials have been prepared from Douiret formation by intercalation of didodecyldimethyl ammonium bromide. This clay has a lower Aptian age and belonged to Douiret (Tataouine) area in the south of Tunisia. This intercalation allowed the improvement of porous texture of the material in question, which supports its use in adsorption of VOCs. Retention properties of such materials towards chlorobenzene have been assessed through the determination of adsorption isotherms using thermogravimetric method. Equilibrium isotherms showed clearly the high efficiency of these new adsorbents toward VOCs.

I. Jarraya, S. Fourmentin, M. Benzina

clay, organoclay, intercalation, Volatile Organic Compounds, adsorption isotherm, modelisation

Pages 139-149

L’oxydation anodique du paraéthylanisole dans l’acétonitrile sur électrode de platine: Etude mécanistique et préparative

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The electrochemical behaviour of substituted benzenes is governed by the nature of the substituants and by the alky chain length. This is illustrated in the case of the anodic oxidation p-ethyl anisole in the solvent acetonitrile. The investigation is carried out by cyclic voltammetry and preparative electrolysis. It has demonstrated the existence of two reaction paths according to the composition of the reaction medium. In anhydrous acetonitrile the reaction involves a nucleus coupling leading to dimers and oligomers. In wet acetonitrile, or when a base such as lutidine is present in the medium, the anodic oxidation led to the substitution-oxidation products of the side chain.

A. Haj Said, F. Matoussi M’halla, S. Roudesli

p-ethyl anisole, anodic oxidation, organic electrochemistry

Pages 151-159

Synthèse, affinement structural et étude spectroscopique par IR et RMN-MAS des hydroxyapatites mixtes calcium-zinc

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Solid solutions of calcium and zinc hydroxyapatite [Ca(10-x)Znx(PO4)6(OH)2] were synthesized by a wet process in a basic medium. They were investigated by X-ray diffraction, chemical analysis, IR and 31P NMR-MAS spectroscopies. The powder X-ray diffraction patterns of the solid products reveal that apatite can be obtained as a unique crystalline phase only for zinc concentration in solution up to 20 atoms percent. Solid state 31P NMR-MAS spectroscopy supposes that zinc atoms are statistically distributed between the two non-equivalent crystallographic sites. IR spectra show the presence of characteristic absorption bands for the apatitic structure and the splitting of the band ca. 340 cm-1 assigned to the “ν3” type stretching of the [M(II)3–OH] owing to the presence of the zinc in the second crystallographic site S(II). Results of spectroscopic study by 31P NMR-MAS and IR were confirmed by the Rietveld structural refinement using Fullprof program.

T. Turki, A. Aissa, H. Agougui, M. Debbabi

Solid solutions, NMR-MAS spectroscopy, Crystallographic sites, Fullprof

Pages 161-172

Synthesis and crystal structure of two [NBun4][Vv4O6(OH)(PhPO3)4] solvates

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The compounds [NBun4][V4O6(OH)(PhPO3)4]·Me2CO (1) and NBun4][V4O6(OH)(PhPO3)4]·0.5MeCN (2) have been isolated as a minor phase in the reaction of phenylphosphonyl dichloride with the mixed isopolyanion [NBun4]4V2W4O19. They crystallize in the triclinic system, space group P–1 with lattice parameters a = 12.6372(17), b = 12.6884(17), c = 19.473(2) Å, α = 104.112(12)°, β = 91.928(11)°, γ = 113.191(9)°, V = 2753.9(7) Å3, Z = 2 for 1 and a = 12.9020(5), b = 20.1755(19), c = 20.634(2) Å, α = 100.062(8)°, β = 99.696(6)°, γ = 96.159(5)°, V = 5160.9(8) Å3, Z = 4 for 2. The hybrid anion structure consists of spherical V/O/P shell of corner-sharing vanadium square pyramids and phenylphosphonate tetrahedra, encapsulating the hydroxo anion (OH-).

H. Driss, F. Bannani, R. Thouvenot, M. Debbabi

Oxovanadium, Organophosphonate, X-Ray structure

Pages 173-178

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