On the dichotomic behavior of the Z-2,4-dinitrophenylhydrazone of 5-amino-3-benzoyl-1,2,4-oxadiazole with acids in toluene and in dioxane/water: Rearrangement versus hydrolysis

Journal of Organic Chemistry

Volumn 69, Issue 25, 2004, Pages 8718-8722

  D'Anna, Francesca ^a   Frenna, Vincenzo ^a   Macalusco, Gabriella ^a   Morganti, Stefano ^b   Nitti, Patrizia ^c   Pace, Vitalba ^a   Spinelli, Domenico ^b   Spisani, Raffaella ^b  

^a UNIVERSITY OF PALERMO   (Italy)

^b UNIVERSITY OF BOLOGNA   (Italy)

^c UNIVERSITY OF TRIESTE   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

ACETIC ACID; BENZENE; CATALYSIS; DERIVATIVES; HYDROLYSIS; NITROGEN COMPOUNDS; SOLVENTS; TOLUENE;

MONONUCLEAR REARRANGEMENT (MRH); TRIAZOLES; TRICHLOROACETIC ACID (TCA);

PHENOLS;

1,2,4 OXADIAZOLE DERIVATIVE; 2,4 DINITROPHENYLHYDRAZONE; 5 AMINO 3 BENZOYL 1,2,4 OXADIAZOLE; DIOXANE DERIVATIVE; PHENYLHYDRAZONE DERIVATIVE; SOLVENT; TOLUENE; TRICHLOROACETIC ACID; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL REACTION; DERIVATIZATION; DRUG ISOLATION; GENE REARRANGEMENT; HYDROLYSIS; PROTON TRANSPORT; QUANTITATIVE ANALYSIS; REACTION ANALYSIS; SYNTHESIS;

EID: 10044262175     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo048803i     Document Type: Article

References (41)

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28. The widespread importance of synthetic methodologies based on the use of heterocycles could be easily envisaged by looking at the symposia-in-print on this topic. E.g., in the past decade, Tetrahedron published four symposia-in-print: (1) Katritzky, A. R., Ed. Novel applications of heterocycles in synthesis. Tetrahedron 1996. Alexakis, A., Ed. Heterocycles in asymmetric synthesis. Tetrahedron 1998. Howell, A. R., Ed. Strained heterocycles as intermediates in organic synthesis. Tetrahedron 2002. Florio, S., Ed. Oxiranyl and aziridinyl anions as reactive intermediates in synthetic organic chemistry. Tetrahedron 2003. Very recently, Chemical Reviews dedicated an entire issue to heterocycles (Katritzky, A. R., Ed. Chem. Rev. 2004, 104 (5)), and several papers were concerned with syntheses of heterocycles as well as their uses as synthones.
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32. - is an operational proton-concentration scale used in dioxane/ water (for details, see ref 2a).
33. By using computations at the DFT level, we have confirmed that in 5-amino-1,2,4-oxadiazole the most basic center is N(4).
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36. In principle, the presence of the third-order pathway could perhaps be in some way favored by the significant association between TCA molecules in toluene, but the direct intervention of the dimeric acid as such could be reasonably excluded considering its very low effective acidic character. The behavior of organic acids in water and in benzene or toluene has been investigated by several authors (see: Gelb, R. I.; Alper, J. S. Anal. Chem. 2000, 72, 1322-1327. Steigman, J.; Cronkright, W. J. Am. Chem. Soc. 1970, 92, 6729-6736; Spectrochim. Acta, Part A 1970, 26, 1805-1811).
37. In principle, the presence of the third-order pathway could perhaps be in some way favored by the significant association between TCA molecules in toluene, but the direct intervention of the dimeric acid as such could be reasonably excluded considering its very low effective acidic character. The behavior of organic acids in water and in benzene or toluene has been investigated by several authors (see: Gelb, R. I.; Alper, J. S. Anal. Chem. 2000, 72, 1322-1327. Steigman, J.; Cronkright, W. J. Am. Chem. Soc. 1970, 92, 6729-6736; Spectrochim. Acta, Part A 1970, 26, 1805-1811).
38. In principle, the presence of the third-order pathway could perhaps be in some way favored by the significant association between TCA molecules in toluene, but the direct intervention of the dimeric acid as such could be reasonably excluded considering its very low effective acidic character. The behavior of organic acids in water and in benzene or toluene has been investigated by several authors (see: Gelb, R. I.; Alper, J. S. Anal. Chem. 2000, 72, 1322-1327. Steigman, J.; Cronkright, W. J. Am. Chem. Soc. 1970, 92, 6729-6736; Spectrochim. Acta, Part A 1970, 26, 1805-1811).
39. 4b = 82 has been calculated].
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